Nonionic glycasuccinimide surfactants and a process for their manufacture

ABSTRACT

The present invention relates to a new class of carbohydrate based nonionic surfactant, i.e., alkyl and alkenyl glycasuccinimide, and a process for their manufacture.

TECHNICAL FIELD

The present invention is related to a new class of carbohydrate basednonionic surfactant, specifically alkyl- and alkenyl glycasuccinimidecompounds and a process for their manufacture.

BACKGROUND OF THE INVENTION

The demand for mild, biodegradable, environmentally friendly surfactantshas been steadily rising. In general, most surfactants are based on, orderived from petrochemicals. Since these materials can have handling,storage and environmental hazards associated with them, it would be mostdesirable to use surfactants which are instead derived fromagriculturally grown materials, such as carbohydrates. These naturallyoccurring compounds represent a source of renewable raw materials thatare readily available, inexpensive, biodegradable, aquatically favorableand optically pure.

A new class of carbohydrate based surfactant has now been found,specifically nonionic alkyl- and alkenyl glycasuccinimide surfactantsand a process for their manufacture. These compounds were found to havesurfactant properties equal to, or better than, other well knownnonionic surfactants based on petrochemicals, thereby indicating thatthey are viable sound alternatives to traditional petrochemicalsurfactants.

BACKGROUND ART

An alkyl- or alkenyl glycasuccinimide is defined as an alkyl- or alkenylimide of an 1-amino-1-deoxyalditol, 1-amino-1,6-dideoxyalditol or2-amino-2-deoxyketitol, which in turn, is defined as a sugar substancein which the pseudoaldehyde or pseudoketose group, generally found atthe C₁ or C₂ position of the sugar, has been reduced to an amino groupthrough a reductive amination reaction with ammonia and hydrogen in thepresence of a metal catalyst such as nickel. The reaction is typicallydone in water or organic solvent, but is usually done in a mixture ofboth. Methods of preparing such glycamines are well known in the art andare described in the J. Chem. Soc. 1682, (1922) to Ling et al.; J. Amer.Chem. Soc. 62, 3315, (1940) to Wayne et al., 72, 54 16, (1950) to Hollyet al., 79, 3541, (1957) to Kagan et al.; Methods in Carbohydr. Chem. 2,79, (1963) to Long et al.; U.S. Pat. No. 2,016,962 to Flint et al., U.S.Pat. No. 2,621,175 to Holly et al.; and EP Application No. 0,536,939 toBeck all of which are incorporated herein by reference.

An alkyl- or alkenyl glycasuccinimide can also be defined as an alkyl-or alkenyl imide of a Z-amino-Z-deoxyalditol (hydrogenated aldosamine orketosamine), wherein Z is from about 2 to about 8, which in turn, isdefined as a sugar substance in which the pseudoaldehyde or pseudoketosegroup, generally found at the C₁ or C₂ position of the sugar, has beenreduced to a hydroxyl group with hydrogen in the presence of a metalcatalyst such as nickel or platinum or a metal reducing agent such assodium borohydride. The reaction is typically done in water. Methods ofpreparing such glycamines are well known in the art and are described inthe J. Biol. Chem. 120, 577, (1937) to Levene et al.; Helv. Chim. Acta.20, 627, (1937) to Karrer et al.; Chem. Ber. 102, 459, (1969) to Paulsenet al.; and U.S. Pat. No. 4,307,072 to Smith all of which areincorporated herein by reference.

An alkyl- or alkenyl glycasuccinimide can be further defined as analkyl- or alkenyl imide of a Z-amino-Z-deoxyaldose,Z-amino-Z-deoxy-ketose, Z-amino-Z-deoxyglycoside, wherein Z is fromabout 1 to about 8. Methods of preparing or isolating such glycaminesare well known in the art and are described in Adv. Carbohydr. Chem. 7,247, (1957) to Foster et al., 13, 189, (1958) to Jeanloz,; Methods inCarbohydr. Chem. 1,228, (1962) to Stacey et al.; Chem. Ber. 103, 1599,(1970) to Paulsen et al.; Can. J. Chem. 46, 1586, (1968) to Sowa et al.;J. Am. Chem. Soc. 81, 3716, (1959) to Wolfrom et al.; Helv. Chim. Acta46, 282, (1963) to Hardegger et al., 40, 342, (1957) to Druey et al.;Ann. 148, 600, (1956) to Kuhn et al,; and J. Org. Chem. 26, 603, (1961)to Zaugg all of which are incorporated herein by reference.

A glycasuccinimide may be based on carbohydrates comprising onesaccharide unit (e.g., ribosuccinimides, glucosuccinimides,2-deoxy-2-aminosorbitolsuccinimides, glucoheptosuccinimides orfructosuccinimides), two saccharide units (e.g., lactosuccinimides,maltosuccinimides or cellobiosuccinimides), three saccharide units(e.g., maltotriosuccinimides or cellotriosuccinimides) or they may bebased on compounds comprising more than three saccharide units (e.g.,maltoheptosuccinimides). It should be noted that any carbohydrate can beused as long as the sugar has an amino group or a pseudoaldehyde orpseudoketose group available for reduction to an amino group.

While certain alkyl- and alkenyl sugar succinate esters are known in theart, there is no teaching or suggestion of alkyl- and alkenyl sugarsuccinate imides (glycasuccinimides) of the present invention assurface-active agents.

U.S. Pat. No. 2,613,206 to Caldwell teaches the manufacture and use ofalkyl- and alkenyl starch succinate esters of the formula: ##STR1##wherein:

R represents a CH₂ CH (dimethylene) or CH₂ CH₂ CH (trimethylene) group;and

R₁ represents an alkyl, alkenyl, aralkyl or aralkenyl group having 1 to18 carbon atoms.

The alkyl- and alkenyl starch succinate esters are prepared by thereaction of starch with alkyl- or alkenyl succinic or glutaric anhydridein the presence of a base catalyst. The reaction is preferably performedin water, but optionally may be performed in a near dry state (5% to 20%water) or in an organic solvent such as benzol. These compounds areanionic in nature and are said to be useful as free flowing agents foroffset dry spray printing applications, as carriers for insecticidepowders, as delustering agents for cellulase acetate rayons or lacquers,as rubber finishing aids and as water repellents for textile sizing andfinishing. There is clearly no teaching or suggestion of the alkyl- andalkenyl glycasuccinimide compounds of the present invention assurface-active agents. Furthermore, the alkyl- and alkenylglycasuccinimide compounds of the present invention are nonionic innature and are completely different structurally.

U.S. Pat. No. 2,661,349 to Caldwell et al. teaches the manufacture anduse of alkyl- and alkenyl polysaccharide succinate esters of theformula: ##STR2## wherein: polysaccharide represents starch, cellulose,methylcellulose or dextrin;

R₂ represents a CH₂ CH (dimethylene) or CH₂ CH₂ CH (trimethylene) group;and

R₃ represents an alkyl, alkenyl, or aralkyl or an aralkenyl group having5 to 18 carbon atoms.

The alkyl- and alkenyl polysaccharide succinate esters are prepared bythe reaction of a polysaccharide with alkyl or alkenyl succinic orglutaric anhydride in the presence of a base catalyst. The reaction ispreferably performed in water, but optionally may be performed in thenear dry state (5% to 20% water) or in an organic solvent such asbenzol, pyridine or toluene. These compounds are anionic in nature andare said to be useful as emulsifying and thickening agents. There isclearly no teaching or suggestion of the alkyl- and alkenylglycasuccinimide compounds of the present invention as surface-activeagents. Furthermore, the alkyl- and alkenyl glycasuccinimide compoundsof the present invention are nonionic in nature and are completelydifferent structurally.

U.S. Pat. No. 2,868,781 and J. Am. Oil Chemists Soc., 38, 410 (1961) toGaertner et al. teaches the manufacture and use of alkyl- and alkenyldisugar succinate esters of the formula:

Sugar-OOC-R₄ -COO-Sugar

wherein:

sugar represents glucose, fructose, methyl α-D-glucoside, sorbitol,sucrose, methyl γ-glucoside, L-sorbose, maltose, lactose, L-xylulose,γ-methyl fructoside, D-mannitol, D-arabitol, xylitol, starch or dextrinand;

R₄ represents an alkyl-CHCH₂, alkenyl-CHCH₂ or alkoxy CHCH₂ group having5 to 20 carbon atoms.

The alkyl- and alkenyl disugar succinate esters are prepared by thereaction of excess sugar with alkyl- or alkenyl succinic acid oranhydride in the presence of a base catalyst and solvent such asdimethylformamide, pyridine or dimethylsulfoxide. These compounds aresaid to be useful as surface-active agents. There is clearly no teachingor suggestion of the alkyl- and alkenyl glycasuccinimide compounds ofthe present invention which are completely different structurally.

U.S. Pat. No. 2,903,382 to Beris teaches a method of waterproofingcellulosic fabrics using alkenyl succinic acid or anhydride to producealkenyl cellulose succinate esters of the formulas. ##STR3## wherein:cellulose represents cellulosic textiles such as cotton, mercerizedcotton or linen;

R₅ represents a CH₂ CH group; and

R₆ represents an alkenyl group having 19 to 35 carbon atoms.

The alkenyl cellulose succinate esters are prepared by impregnatingcellulose fibers with alkenyl succinic acid or anhydride in the presenceof base catalyst and water or solvent such as isopropanol, benzene,toluene, chloroform and carbon tetrachloride. There is clearly noteaching or suggestion of the alkyl- and alkenyl glycasuccinimidecompounds of the present invention which are useful as surface-activeagents.

U.S. Pat. Nos. 2,973,353 and 3,053,830 to Gaertner, teaches themanufacture and use of alkyl- and alkenyl monosugar succinate esters ofthe formula: ##STR4## wherein: sugar represents glucose, fructose,methyl α-D-glucoside, sorbitol, sucrose, maltose, lactose, L-sorbose,L-xylulose, β-methyl D-glucoside, β-methyl fructoside, γ-methylL-fructoside or other glycosides; R₇ represents an alkyl or alkenylgroup having 6 to 20 carbon atoms; and M represents hydrogen or a saltforming cation.

The alkyl- and alkenyl monosugar succinate esters are prepared by thereaction of sugar with alkyl- or alkenyl succinic acid or anhydride inthe presence of a base catalyst. The reaction is usually performed inthe presence of an organic solvent such as dimethylformamide,diethylformamide, dipropylformamide, dimethylacetamide,diethylacetamide, dimethylpropionamide, dimethylsulfoxide,diethylsulfoxide or pyridine. These compounds are said to be useful asemulsifying agents, wetting agents and foaming agents. There is clearlyno teaching or suggestion of the alkyl- and alkenyl glycasuccinimidecompounds of the present invention which are useful as surface-activeagents. Also, the alkyl- and alkenyl monosugar succinate esters of U.S.Pat. Nos. 2,973,353 and 3,053,830 are anionic in nature where as thecompounds of this invention are nonionic in nature.

U.S. Pat. No. 3,219,657 to Gaertner, teaches the manufacture and use ofalkyl- and alkenyl saccharide polydicarboxylate half-esters of theformula: ##STR5## wherein: Z represents glucose, fructose, methylα-D-glucoside, sorbitol, β-methyl D-glucoside, β-methyl fructoside,γ-methyl D-glucoside, γ-methyl L-fructoside, D-mannitol, D-arabitol,xylitol, sucrose, maltose or lactose;

R₈ is an alkyl or alkenyl group having 6 to 20 or more carbons; and

n is at least 2 up to 8.

The alkyl- and alkenyl saccharide polydicarboxylate esters are preparedby the reaction of sugar with excess alkyl- or alkenyl succinicanhydride in the presence of base catalyst and solvent such asdimethylformamide, pyridine or dimethylsulfoxide. The reaction may bepreformed in a melt, however, browning reactions or decomposition of thesugar substrate often occurs, yielding compounds that are dark in color.There is clearly no teaching or suggestion of the alkyl- and alkenylglycasuccinimide compounds of the present invention which are isolatedin high yield as white crystalline solids.

JP 4,288,092 to Nakajima teaches a process for the manufacture ofalkenyl sugar succinate esters which are useful as emulsifiers,detergents, protective colloids and cosmetic bases for toiletryarticles. Useful sugar substrates include glucose, mannose, allose,altrose, talose, galactose, idose, gulose, fructose, tagatose, ribose,arabinose, xylose, lyxose, sorbose, ribulose, xylulose, psicose,rhamnose, sucrose, maltodextrin, cyclodextrin, isomaltodextrin,cellooligosaccharide, galactooligosaccharide, mannooligosaccharide,hydrolyzed starch, caramelized sugar, glucosamine, galactosamine,condurosamine, mannosamine, gulosamine, kanosamine, glucuronic acid,guluronic acid, galacturonic acid, mannuronic acid, glycerol,erythritol, ribitol, arabinitol, mannitol, sorbitol, glucitol, dulcitoland starch syrups. Although JP 4,288,092 describes the use of certainglycamines as useful starting materials (substrates), this patent failsto teach or contemplate the alkyl- and alkenyl glycasuccinimides of thepresent invention which are structurally different. Also, the process inJP 4,288,092 requires the use of water and organic solvents such asalcohol or acetone, and produces surfactants that are anionic in naturenot nonionic in nature as described in this disclosure.

Lastly, it should be noted that all the above processes require costlyorganic solvents, some of which have handling, storage and environmentalhazards associated with them. The process of this invention can also useorganic solvents, however, it is not required making this process moreviable and commercially feasible. Also, as seen in comparative Example1, the compounds prepared by previous methods, are generally isolated asthick colored syrups which are difficult to handle and isolate. Thealkyl- and alkenyl glycasuccinimide compounds of this invention areisolated as crystalline solids in good yield, high purity, and desirablecolor.

Thus, the ability to find a naturally derived, environmentally friendly,biodegradable, solid sugar based nonionic surfactant and a viable,cost-effective, commercially feasible method for their manufacture is asignificant achievement.

Accordingly, it is an objective of the present invention to providenovel nonionic alkyl- and alkenyl glycasuccinimide compounds assurface-active agents.

It is another object of the present invention to provide naturallyderived, cost-effective nonionic alkyl- and alkenyl glycasuccinimidesurfactants.

It is another object of the present invention to provide nonionic alkyl-and alkenyl glycasuccinimide surfactants that dissolve readily and foamwell in water.

It is still another object of the present invention to provide nonionicalkyl- and alkenyl glycasuccinimide surfactants that have a low surfacetension and a favorable critical micelle concentration in water.

It is still another object of the present invention to provide a viable,commercially feasible process for the manufacture of nonionic alkyl- andalkenyl glycasuccinimide surfactants.

It is a final object of the present invention to prepare solid nonionicalkyl- and alkenyl glycasuccinimide surfactants in good yield, highpurity, and desirable color without hydroxyl group protection,oligomerization or polymerization. These and other objects will becomereadily apparent from the detailed description which follows.

SUMMARY OF THE INVENTION

In one embodiment of the invention, the invention relates to a new classof carbohydrate based nonionic surfactant, specifically novel nonionicalkyl- and alkenyl glycasuccinimide surfactants.

In another embodiment of the invention, the invention relates to a newand improved process for preparing such surfactants. The process is animprovement over the art known processes for the preparation of alkyl-and alkenyl sugar succinate esters, wherein the improvement comprisesreacting an alkyl- or alkenyl succinic acid ester or anhydride directly(without a solvent) with a glycamine in the presence of a base catalyst.This embodiment of the invention is particularly directed to preparingsolid alkyl- and alkenyl glycasuccinimide compounds in good yield, highpurity and desirable color without hydroxyl group protection,oligomerization or polymerization and so the process of manufacture iscommercially feasible and economically viable.

The alkyl- and alkenyl glycasuccinimide compounds of the invention havesurfactant properties equal to, or better than, other well knownnonionic surfactants based on petrochemicals, thereby indicating thatthey are viable sound alternatives to traditional petrochemicalsurfactants.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a new class of environmentally friendly"green" nonionic carbohydrate based surfactant. In particular, oneembodiment of the invention describes novel nonionic alkyl- and alkenylglycasuccinimide surfactants.

In another embodiment of the invention, a new and improved process forthe manufacture of alkyl- and alkenyl glycasuccinimide surfactants isdescribed.

In general, the nonionic alkyl- and alkenyl glycasuccinimide surfactantsare of the formula: ##STR6## wherein:

A represents the following structures which are attached to thesuccinate ring via the nitrogen (N) atom; ##STR7##

G is hydrogen (H), a SO₃ M, PO₃ M₂, (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃O)_(b) H group, a mono-, di-, oligo- or polysaccharide or mixturesthereof;

M is hydrogen (H), an alkali metal, alkaline earth metal, ammonium,alkyl substituted ammonium or mono-, di-, trialkanolammonium grouphaving about 1 to about 5 carbon atoms;

W is a CH₂ group, oxygen atom (O) or mixtures thereof;

X is hydrogen (H), an alkyl group having about 1 to about 4 carbon atomsor mixtures thereof;

Y is a NR₁₀, +N(R₁₀)₂, O, S, SO, SO₂, COO, OOC, CONR₁₀, NR₁₀ CO group ormixtures thereof;

Z is a CH═CH, CH₂ CH₂ group or mixtures thereof;

R₉ is a straight or branched chain saturated or unsaturated hydrocarbonwhich may be unsubstituted or substituted with an aromatic,cycloaliphatic or mixed aromatic radical having about 1 to about 31carbon atoms;

R₁₀ is hydrogen (H), a hydroxylalkyl group having about 1 to about 6carbon atoms, a straight or branched chain, saturated or unsaturatedhydrocarbon which may be unsubstituted or substituted with an aromatic,cycloaliphatic or mixed aromatic aliphatic radical having about 1 toabout 8 carbon atoms;

R₁₁ is hydrogen (H), or an alkyl, alkenyl or hydroxyalkyl group havingabout 1 to about 6 carbon atoms;

R₁₂ is hydrogen (H), or an alkyl, alkenyl or hydroxyalkyl group havingabout 1 to about 6 carbon atoms;

a=0-35;

b=0-35;

c=1-3;

d=1-5;

e=0-35;

m=0-8;

n=1-6;

o=0-2;

p=0-4;

q=0-3;

r=0-3;

and s=0-1.

preferably:

A represents the following structures which are attached to thesuccinate ring via the nitrogen (N) atom; ##STR8##

G is hydrogen (H), a (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) H group, amono- di- or oligosaccharide or mixtures thereof;

W is a CH₂ group, oxygen atom (O) or mixtures thereof;

X is hydrogen (H), an alkyl group having about 1 to about 3 carbon atomsor mixtures thereof;

Y is a NR₁₀, +N(R₁₀)₂, O, COO, OOC group or mixtures thereof;

Z is a CH═CH, CH₂ CH₂ group or mixtures thereof;

R₉ is a straight or branched chain saturated or unsaturated hydrocarbonwhich may be unsubstituted or substituted with an aromatic,cycloaliphatic or mixed aromatic radical having about 2 to about 25carbon atoms;

R₁₀ is hydrogen (H), a hydroxylalkyl group having about 1 to about 4carbon atoms, a straight or branched chain, saturated or unsaturatedhydrocarbon radical having about 1 to about 5 carbon atoms;

R₁₁ is hydrogen (H), or an alkyl, alkenyl or hydroxyalkyl group havingabout 1 to about 5 carbon atoms;

R₁₂ is hydrogen (H), or an alkyl, alkenyl or hydroxyalkyl group havingabout 1 to about 5 carbon atoms;

a=0-25;

b=0-25;

c=1-3;

d=1-4;

e=0-25;

m=0-7;

n=1-5;

o=0-2;

p=0-3;

q=0-2;

r=0-2;

and s=0-1.

More preferably:

A represents the following structures which are attached to thesuccinate ring via the nitrogen (N) atom; ##STR9##

G is hydrogen (H), a (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) H group, amonosaccharide or mixtures thereof;

X is hydrogen (H), an alkyl group having about 1 to about 2 carbon atomsor mixtures thereof;

Y is an oxygen atom (O) or a COO or OOC group or mixtures thereof;

Z is a CH═CH, CH₂ CH₂ group or mixtures thereof;

R₉ is a straight or branched chain saturated hydrocarbon radical havingabout 3 to about 23 carbon atoms;

R₁₂ is hydrogen (H), or an alkyl, alkenyl or hydroxyalkyl group havingabout 1 to about 4 carbon atoms;

a=0-15;

b=0-15;

c=1-2;

d=1-4;

e=0-15;

m=0-5;

n=1-5;

o=0-1;

p=0-2;

and q=0-2.

A specific example of a monosaccharide alkyl glycasuccinimide compoundof the invention is dodecyloxy D-glucosuccinimide having the formula:##STR10## wherein based on formula (I) above: ##STR11## G=hydrogen (H);R₉ =C₁₀ H₂₁ ;

W=oxygen (O);

Z=CH₂ CH₂ ;

c=1;

e=0;

m=0;

and n=4.

Another specific example of a monosaccharide alkyl glycasuccinimidecompound of the invention is tetradecyloxytri(oxyethyl)D-glucosuccinimide, also known as tetradecyloxy(triethylene glycol)ether D-glucosuccinimide or as tetradecyloxy(trioxyethylene)D-glucosuccinimide having the

formula: ##STR12## wherein based on formula (I) above: ##STR13##G=hydrogen (H); R₉ =C₁₂ H₂₅ ;

W=oxygen (O);

X=hydrogen (H);

Y=oxygen (O);

Z=CH₂ CH₂ ;

c=1;

d=2;

e=3;

m=0;

and n=4.

Yet another specific example of a monosaccharide alkyl glycasuccinimidecompound of the invention is dodecyl D-glucosuccinimide tetraoxyethyleneether, also known as dodecyl D-glucosuccinimide tetraethylene glycolether or more generally as polyoxyethylene (4) dodecylD-glucosuccinimide having the formula: ##STR14## wherein based onformula (I) above: ##STR15## G=hydrogen (H) or (CH₂ CH₂ O)_(a) H group;R₉ =C₉ H₁₉ ;

W=CH₂ ;

a=can vary from about 1 to about 8 for a total average of 4;

c=1;

e=0;

m=0;

and n=4.

A specific example of a monosaccharide alkenyl glycasuccinimide compoundof the invention is decenyl D-glucosuccinimide also known as decenyl1-imino-1-deoxy D-glucitol succinate or decenyl 1-imino-1-deoxyD-sorbitol succinate having the formula: ##STR16## wherein based onformula (I) above: ##STR17## G=hydrogen (H); R₉ =C₇ H₁₅ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

and n=4.

Another specific example of a monosaccharide alkenyl glycasuccinimidecompound of the invention is dodecenyl L-rhamnosuccinimide also know asdodecenyl 1-imino-1,6-dideoxy L-rhamnitol succinate or dodecenyl1-imino-1,6-dideoxy L-mannitol succinate having the formula: ##STR18##wherein based on formula (I) above: ##STR19## G=hydrogen (H); R₉ =C₉ H₁₉;

W=CH₂ ;

Z=CH═CH;

c=l;

e=0;

and n=4.

A specific example of a cyclic monosaccharide alkenyl glycasuccinimidecompound of the invention is decenyl D-sorbitansuccinimide having theformula: ##STR20## wherein based on formula (I) above: ##STR21##G=hydrogen (H); R₉ =C₇ H₁₅ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

p=1;

and q=1.

Another specific example of a cyclic monosaccharide alkenylglycasuccinimide compound of the invention is dodecenyl 1-imino-1-deoxyD-fructopyranosyl succinate having the formula: ##STR22## wherein basedon formula (I) above: ##STR23## G=hydrogen (H); W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

o=1;

and p=0.

Yet another specific example of a cyclic monosaccharide alkenylglycasuccinimide compound of the invention is dodecenyl 6-imino-6-deoxyα,β-D-methylglucopyranoside succinate having the formula: ##STR24##wherein based on formula (I) above: ##STR25## G=hydrogen R₉ C₉ H₁₉ ;

R₁₂ =CH₃ ;

W=CH₂ ;

Z=CH═CH;

C=1;

e=0;

o=1;

and p=1.

A specific example of a disaccharide alkyl glycasuccinimide compound ofthe invention is tetradecyl D-maltosuccinimide having the formula:##STR26## wherein based on formula (I) above: ##STR27## G=hydrogen (H)or glucose; R₉ =C₁₁ H₂₃ ;

W=CH₂ ;

Z=CH₂ CH₂ ;

c=1;

e=0;

m=0;

and n=4.

A specific example of a disaccharide alkenyl glycasuccinimide compoundof the invention is dodecenyl D-lactosuccinimide having the formula:##STR28## wherein based on formula (I) above: ##STR29## G=hydrogen (H)or galactose; R₉ =C₉ H₁₉ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

and n=4.

Other examples of compounds of the invention are set forth below:

alkyl and alkenyl D-erythrosuccinimide

alkyl and alkenyl D-threosuccinimide

alkyl and alkenyl D-ribosuccinimide

alkyl and alkenyl D-arabinosuccinimide

alkyl and alkenyl D-xylosuccinimide

alkyl and alkenyl D-lyxosuccinimide

alkyl and alkenyl D-allosuccinimide

alkyl and alkenyl D-altrosuccinimide

alkyl and alkenyl D-idosuccinimide

alkyl and alkenyl D-talosuccinimide

alkyl and alkenyl D-glucosuccinimide

alkyl and alkenyl L-glucosuccinimide

alkyl and alkenyl D-galactosuccinimide

alkyl and alkenyl L-galactosuccinimide

alkyl and alkenyl D-mannosuccinimide

alkyl and alkenyl D-gulosuccinimide

alkyl and alkenyl D-fructosuccinimide

alkyl and alkenyl L-fructosuccinimide

alkyl and alkenyl D-sorbosuccinimide

alkyl and alkenyl L-sorbosuccinimide

alkyl and alkenyl D-isomaltosuccinimide

alkyl and alkenyl D-isomaltsuccinimide

alkyl and alkenyl D-isomaltulosuccinimide

alkyl and alkenyl D-trehalulosuccinimide

alkyl and alkenyl D-ribulosuccinimide

alkyl and alkenyl D-xylulosuccinimide

alkyl and alkenyl D-3-ketosucrosuccinimide

alkyl and alkenyl D-leucrosuccinimide

alkyl and alkenyl D-lactulosuccinimide

alkyl and alkenyl D-psicosuccinimide

alkyl and alkenyl D-rhamnosuccinimide

alkyl and alkenyl D-maltosuccinimide

alkyl and alkenyl L-maltosuccinimide

alkyl and alkenyl D-lactosuccinimide

alkyl and alkenyl L-lactosuccinimide

alkyl and alkenyl D-melibiosuccinimide

alkyl and alkenyl D-cellobiosuccinimide

alkyl and alkenyl D-cellulosuccinimide

alkyl and alkenyl D-dextrosuccinimide

alkyl and alkenyl D-glucosuccinimide monooxyethylene ether

alkyl and alkenyl D-glucosuccinimide dioxyethylene ether

alkyl and alkenyl D-glucosuccinimide trioxyethylene ether

alkyl and alkenyl D-glucosuccinimide pentaoxyethylene ether

alkyl and alkenyl D-glucosuccinimide hexaoxyethylene ether

alkyl and alkenyl D-glucosuccinimide octaoxyethylene ether

alkyl and alkenyl D-glucosuccinimide nonaoxyethylene ether

alkyl and alkenyl D-glucosuccinimide decaoxyethylene ether

alkyl and alkenyl D-glucosuccinimide tetraoxypropylene ether

alkyloxy(monooxyethylene) D-glucosuccinimide

alkyloxy(dioxyethylene) D-glucosuccinimide

alkyloxy(trioxyethylene) D-glucosuccinimide

alkyloxy(pentaoxyethylene) D-glucosuccinimide

alkyloxy(heptaoxyethylene) D-glucosuccinimide

alkyloxy(decaoxyethylene) D-glucosuccinimide

alkyloxy(pentaoxypropylene) D-glucosuccinimide

alkyloxyethylamino D-glucosuccinimide

alkyloxyethylamido D-glucosuccinimide

Wherein the alkyl or alkenyl group contains from about 1 to about 31carbon atoms; preferably from about 2 to about 25 carbon atoms, evenmore preferably from about 3 to about 23 carbon atoms.

The G group can be hydrogen (H), a SO₃ M, PO₃ M₂, (CH₂ CH₂ O)_(a) H or(CH₂ CHCH₃ O)_(b) H group, a mono-, di-, oligo- or polysaccharide ormixtures thereof. Examples of M include, but are not limited tohydrogen, sodium, potassium, magnesium, ammonium, monoethanolammonium,diethanoiammonium, triethanolammonium and the like.

Examples of suitable saccharides that can be reduced to a glycamineinclude aldotrioses, aldotetroses, aldopentoses, aldohexoses,6-deoxyaldohexoses, aldoheptoses, ketotrioses, ketopentoses,ketohexoses, ketoheptoses, ketooctoses and ketononoses. Specific exampleof saccharides that fall within the above classes include, but are notlimited to glyceraldehyde, erythrose, threose, ribose, arabinose,xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose,galactose, talose, 6-deoxyallose, 6-deoxyaltrose, 6-deoxyglucose,6-deoxygulose, 6-deoxytalose, fucose, rahmnose, glycergalactoheptose,glycerglucoheptose, glycermannoheptose, 1,3-dihydroxy-2-propanone,erythrulose, ribulose, xylulose, psicose, fructose, sorbose, tagatose,alloheptose, altro-3-heptulose, mannoheptulose, sedoheptulose,taloheptulose, glycerogalactooctulose, glycermannooctulose,erythrogalactononulose, erythroglucononulose, sucrose, lactose, maltose,isomaltose, isomalt, isomaltulose (palatinose), α,α-trehalose,cellobiose, gentiobiose, laminarabiose, xylobiose, inulobiose,mannobiose, chondrosine, 3-ketosucrose, leucrose, lactulose, melibiose,turnanose, trehalose, raffinose, planteose, melezitose, gentianose,maltotriose, cellotriose, panose, starchyose, verbascose,cyclohexaamylose, maltoheptanose, cellodextrin, amylose, amylodextrin,dextran, high dextrose corn syrup, high fructose corn syrup, highmaltose corn syrup, xylans, mannans, starch, hemicellulose andcellulose. The saccharide may be acyclic or cyclic (including furanose,pyranose, septanose rings or mixtures thereof), have the D or Lconfiguration and contain a α or β glycoside group or mixtures thereofat the anomeric position.

If the R₉ group is an aliphatic radical (saturated or unsaturatedhydrocarbon), suitable examples include methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, coco, soya,tallow, tall oil, castor, corn, cottonseed, palm, rapeseed, safflower,sesame, sunflower, fish oil, allyl, hexenyl, heptenyl, octenyl, nonenyl,decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl,hexadecenyl, heptadecenyl, octadecenyl (oleyl), linoleyl and linolenyl.

If the R₁₀ group is an aliphatic radical, suitable examples includemethyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, propenyl,butenyl, pentenyl, hexenyl, heptenyl, octenyl, hydroxymethyl,hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl andhydroxyhexyl.

If the R₁₁ or R₁₂ group is an aliphatic radical, suitable examplesinclude methyl, ethyl, propyl, butyl, pentyl, propenyl, butenyl,pentenyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl andhydroxypentyl.

If the R₉ or R₁₀ is interrupted by an aromatic group, the aromaticradical may be for example, benzyl or aniline. Cycloaliphatic radicalsare exemplified, but not limited to cyclopentyl and cyclohexyl. Suitablemixed aromatic aliphatic radicals are exemplified by benzylpropyl,phenylethyl, phenoxyethyl and vinylbenzyl.

When an amino group is present in the alkyl chain (wherein W=NR₁₀ andR₁₀ is hydrogen), it may be converted to the corresponding salt byreaction with, for example, an organic or inorganic acid such ashydrochloric acid, sulfuric acid, phosphoric acid, boric acid, oxalicacid, malonic acid, glutaric acid, adipic acid, sebacic acid,tricarballylic acid, 1,2,3,4-butanetetracarboxylic acid, itaconic acid,maleic acid, malic acid, fumaric acid, citraconic acid, glutaconic acid,bis(hydroxymethyl)propionic acid, tartaric acid, citric acid, formicacid, lactic acid, acetic acid, benzoic acid, methanesulfonic acid,ethanesulfonic acid, toluenesulfonic acid and the like or by reactionwith, for example, an alkylating or quaternizing agent such aschloromethane, dimethyl sulfate, diethyl sulfate, benzyl chloride andthe like to form a salt or quaternary ammonium compound.

The alkyl- and alkenyl D-glycasuccinimide compounds of the presentinvention can also be ethoxylated, propoxylated or butoxylated withethylene oxide, propylene oxide, butylene oxide or mixtures thereof togive a series of novel polyoxyalkylene sugar based nonionic surfactants.

The alkyl- and alkenyl D-glycasuccinimide compounds of the presentinvention can also be sulfated with chlorosulfonic acid, sulfurtrioxide, sulfur trioxide/Lewis base complexes, oleum, sulfuric acid,sulfamic acid and the like as well as mixtures thereof, to give a seriesof novel sulfated sugar based anionic surfactants.

The alkyl- and alkenyl D-glycasuccinimide compounds of the presentinvention can also be phosphorylated with phophorus oxychloride,phosphorous pentoxide, polyphosphoric acid, phosphoric acid, phosphorustrichloride and the like as well as mixtures thereof, to give a seriesof novel phosphated sugar based esters (mono-, di-, and triesters aswell as mixtures thereof) as anionic surfactants.

In the second embodiment of the invention, a new and improved processfor the manufacture of alkyl- and alkenyl glycasuccinimide surfactantsis described.

It has been found, in accordance with the present invention, that novelalkyl- and alkenyl glycasuccinimide surfactants may be readily preparedby reacting glycamines (sugar-NH₂) with alkyl- or alkenyl succinicanhydrides in the presence of a base catalyst at elevated temperatures(Δ). The invention can be more readily understood when reference is madeto the general equation (A): ##STR30##

The method is especially suitable for the manufacture of alkyl- andalkenyl glycasuccinimide compounds wherein W is preferably CH₂ or anoxygen atom (O); X is preferably hydrogen (H), or an alkyl group havingabout 1 to about 3 carbon atoms; Y is preferably a NR₁₀, +N(R₁₀)₂,oxygen (O) group or mixtures thereof; Z is preferably a CH═CH or CH₂ CH₂group; R₉ is preferably a straight chain saturated hydrocarbon which maybe unsubstituted or substituted with an aromatic, cycloaliphatic ormixed aromatic radical comprising from about 2 to about 25 carbon atoms,R₁₀ is preferably hydrogen (H), a hydroxyalkyl group having about 1 toabout 4 carbon atoms, a straight or branched chain, saturated orunsaturated hydrocarbon radical having about 1 to about 5 carbon atoms;c is preferably 1-3; d is preferably 1-4; and e is preferably 0-25.

Examples of preferred glycamines (1-amino-1-deoxyalditols,2-amino-2-deoxyketitols etc.) most suitable for this method includethose of the formula: ##STR31## wherein G is hydrogen (H), a (CH₂ CH₂O)_(a) H or (CH₂ CHCH₃ O)_(b) H group, a mono-, di-, oligo- orpolysaccharide or mixtures thereof; a and b are each from about 0 toabout 35 and the sum of a and b are from about 0 to about 35; n is fromabout 1 to about 6, m is from about 0 to about 8 and the sum of n and mare from about 0 to about 10. Illustrative of this class include, butare not limited to glyceramine, erythramine, threamine, ribamine,arabinamine, xylamine, lyxamine, aliamine, altramine, glucamine(1-amino-1-deoxyglucitol), mannamine, gulamine, idamine, galactamine,talamine, glucoheptamine (1-amino-1-deoxyglucoheptitol),1-amino-1-deoxyglyceroglucoheptitol,1-amino-1-deoxyglycergalactoheptitol,1-amino-1-deoxyglyceromannoheptitol, 1,3-dihydroxy-2-propylamine,erythrulamine (threulamine or glycerotetrulamine), ribulamine(erythropentulamine), xylulamine (threopentulamine), psicamine,fructamine (levulamine or 2-amino-2-deoxyfructitol), sorbamine(2-amino-2-deoxysorbitol), tagatamine, 2-amino-2-deoxyalloheptulitol,3-amino-3-deoxyaltro-3-heptulitol, 2-amino-2-deoxymannoheptulitol,2-amino-2-deoxysedoheptulitol, 2-amino-2-deoxytaloheptulitol,2-amino-2-deoxyglycerogalactooctulitol,2-amino-2-deoxyglyceromannooctulitol,2-amino-2-deoxyerythrogalactononulitol,2-amino-2-deoxyerythroglucononulitol, lactamine[galactopyranosyl-[β-(1-4)-1-amino-1-deoxyglucitol], maltamine[glucopyranosyl-α-(1-4)- 1-amino-1-deoxyglucitol]isomaltamine-A[glucopyranosyl-α-(1-6)-1-amino-1-deoxyglucitol], isomaltamine-B[glucopyranosyl-α-(1-6)-2-amino-2-deoxyfructitol], isomaltulamine[palatinamine or glucopyranosyl-α-(1-6)-2-amino-2-deoxyfructitol],cellobiamine [glucopyranosyl-α-(1-4)- 1-amino-1-deoxyglucitol],leucramine [glucopyranosyl-α-(1-5)-2-amino-2-deoxyfructitol],gentiobiamine [glucopyranosyl-[β-(1-6)-1-amino-1-deoxyglucitol],laminarbiamine [glucopyranosyl-[β-(1-3)-1-amino-1-deoxyglucitol],xylobiamine [xylo-pyranosyl-[β-(1-4)-1-amino-1-deoxyxylitol],inulobiamine [fructopyranosyl-β-(2-1 )-2-amino-2-deoxyfructitol],mannobiamine [mannopyranosyl-[β-(1-4)-1-amino-1-deoxymannitol],3-ketopalatinamine[3-ketoglucopyranosyl-α(1-6)-2-amino-2-deoxyfructitol],arabinofuranosyl-α-(1-3)-1-amino-1-deoxyarabinitol,galactopyranosyl-α-(1-3)-1-amino-1-deoxygalactitol, maltotriamine[glucopyranosyl-α-(1-4)-glucopyranosyl-α-(1-4)-1-amino-1-deoxyglucitol],cellotriamine[glucopyranosyl-[β-(1-4)-glucopyranosyl-[β-(1-4)-1-amino-1-deoxyglucitol],panosamine[glucopyranosyl-α-(1-6)-glucopyran-osyl-α-(1-4)-1-amino-1-deoxyglucitol],maltoheptamine [glucopyranosyl-α(1-4)-{glucopyranosyl-α-(1-4)₅-amino-1-deoxyglucitol], starchamine, dextramine, cellulamine,2-amino-2-deoxyglucitol (2-amino-2-deoxysorbitol),3-amino-3-deoxyglucitol, 4-amino-4-deoxyglucitol,6-amino-6-deoxy-glucitol, 3-amino-3-deoxyribitol,2-amino-2-deoxygalactitol, 2-amino-2-deoxymannitol,2-amino-2-deoxyallitol, 5-amino-5-deoxyaltritol and6-amino-6-deoxyerythrogalactooctitol.

Examples of other glycamines (1-amino-1,6-dideoxyalditols) suitable forthis method include those of the formula: ##STR32## wherein G ishydrogen (H), a (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) H group, a mono-,di-, oligo- or polysaccharide or mixtures thereof; a and b are each fromabout 0 to about 35 and the sum of a and b are from about 0 to about 35;n is from about 1 to about 6, m is from about 0 to about 8 and the sumof n and m are from about 0 to about 10. Illustrative of this classinclude, but are not limited to 1-amino-1,6-dideoxyallitol,1-amino-l,6-dideoxyaltritol, 1-amino- 1,6-dideoxyglucitol, 1-amino-1,6-dideoxygulitol, 1-amino-1,6-di-deoxytalitol, 1-amino-1,6-dideoxyfucitol and 1-amino-1,6-dideoxyrhamnitol.

Still other examples of glycamines (1-amino-1-deoxyketoses) suitable forthis method include those of the formula: ##STR33## wherein G ishydrogen (H), a (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) H group, a mono-,di-, oligo- or polysaccharide or mixtures thereof; a and b are each fromabout 0 to about 35 and the sum of a and b are from about 0 to about 35;o is from about 0 to about 2 and p is from about 0 to about 4. Theseglycamines are described as Amadori rearrangement products and methodsfor preparing such are disclosed in Methods in Carbohydr. Chem. 2, 99,(1963) to Hodge and Fisher which is incorporated herein by reference.Illustrative of this class include, but are not limited to1-amino-1-deoxyribulose, 1-amino- 1-deoxyxylulose,1-amino-1-deoxypsicose, 1-amino-1-deoxyfructose(1-amino-1-deoxylevulose), 1-amino-1-deoxyfructose hydrochloride,1-amino-1-deoxyfructose acetate salt, 1-amino-1-deoxyfructose oxalatesalt, 1-amino-1-deoxysorbose, 1-amino-1-deoxytagatose,1-amino-1-deoxyalloheptulose, 1-amino-1-deoxymannoheptulose,1-amino-1-deoxysedoheptulose, 1-amino-1-deoxytaloheptulose,1-amino-1-deoxyglycerogalactooctulose,1-amino-1-deoxyglyceromannooctulose,1-amino-1-deoxyerythrogalactononulose,galactopyranosyl-[β-(1-4)-1-amino-1-deoxyfructose,glucopyranosyl-α-(1-4)-1-amino-1-deoxyfructose,glucopyranosyl-α-(1-4)-glucopyranosyl-α-(1-4)-1-amino-1-deoxyfructoseand glucopyranosyl-α-(1-4)-{glucopyranosyl-α-(1-4)}₄-1-amino-1-deoxyfructose.

Still other examples of glycamines (Z-amino-Z-deoxyaldoses) suitable forthis method include those of the formula: ##STR34## wherein G ishydrogen (H), a SO₃ M, PO₃ M₂, (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) Hgroup, a mono-, di-, oligo- or polysaccharide or mixtures thereof; M ishydrogen (H), an alkali metal, alkaline earth metal, ammonium, alkylsubstituted ammonium or mono-, di-, trialkanolammonium group with about1 to about 5 carbon atoms; a and b are each from about 0 to about 35 andthe sum of a and b are from about 0 to about 35; p and q are each fromabout 0 to about 3, r is from about 0 to about 4, s is from about 0 toabout 1 and the sum of p, q and r are from about 0 to about 6.Illustrative of this class include, but are not limited to3-amino-3-deoxyribose, glucosamine (chitosamine or2-amino-2-deoxyglucose), glucosamine hydrochloride, glucosamine acetate(2-acetamido-2-deoxyglucose), glucosamine-2-sulfate,glucosamine-3-sulfate, glucosamine-6-sulfate, glucosamine-2,3-disulfate,glucosamine-2,6-disulfate, glucosamine- 1-phosphate,glucosamine-6-phosphate, kanosamine (3-amino-3-deoxyglucose),4-amino-4-deoxyglucose, 2-amino-2,6-dideoxyglucose,3-amino-3,6-dideoxyglucose, mannosamine (2-amino-2-deoxymannose),mycosamine (2-amino-2,6-dideoxymannose), 3-amino-3,6-dideoxymannose,gulosamine (2-amino-2-deoxygulose), galactosamine (chondrosamine or2-amino-2-deoxygalactose), fucosamine (2-amino-2,6-dideoxygalactose),3-amino-3,6-dideoxygalactose, talosamine (2-amino-2-deoxytalose),pneumosamine (2-amino-2,6-dideoxytalose), daunosamine(3-amino-2,3,6-trideoxylyxohexose), chitobiose[2-amino-2-deoxy-4-O-(2-amino-2-deoxy-[β-glucopyranosyl)glucopyranose],2-amino-2-deoxy-4-O-(α-glucopyranosyl)glucopyranose,2-amino-2-deoxy-4-O-(2-amino-2-deoxy-[β-glucopyranosyl)₄ glucopyranose,chitin and chitosan.

Still other examples of glycamines (1-amino-1-deoxyaldoses and2-amino-2-deoxyketoses) suitable for this method include those of theformula: ##STR35## wherein G is hydrogen (H), a (CH₂ CH₂ O)_(a) H or(CH₂ CHCH₃ O)_(b) H group, a mono-, di-, oligo- or polysaccharide ormixtures thereof; a and b are each from about 0 to about 35 and the sumof a and b are from about 0 to about 35; o is from about 0 to about 2and p is from about 0 to about 4. Illustrative of this class include,but are not limited to 1-amino-1-deoxyribose, 1-amino-1-deoxyxylose,1-amino- 1-deoxyglucose, 1-amino- 1-deoxymannose, 1-amino-1-deoxygulose,1-amino-1-deoxyidose, 1-amino- 1-deoxygalactose,1-amino-1-deoxyglucoheptose, 1-amino-1-deoxyglyceroglucoheptose,2-amino-2-deoxyfrucose, 2-amino-2-deoxysorbose, 1-amino-1-deoxylactose[galactopyranosyl-β-(1-4)-1-amino- 1-deoxyglucose],1-amino-1-deoxymaltose [glucopyranosyl-α-(1-4}-₅-1-amino-1-deoxyglucosel, 1-amino-1-deoxymaltotriose][glucopyranosyl-α-(1-4)-glucopyranosyl-α-(1-4)-1-amino-1-deoxyglucose]and 1-amino-1-deoxymaltoheptose[glucopyran-osyl-α-(1-4)-{glucopyranosyl-α-(1-4)}₅-1-amino-1-deoxyglucose].

Still other examples of glycamines (Z-amino-Z-deoxyglycosides) suitablefor this method include those of the formula: ##STR36## wherein G ishydrogen (H), a SO₃ M, PO₃ M₂, (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) Hgroup, a mono-, di-, oligo- or polysaccharide or mixtures thereof; M ishydrogen (H), an alkali metal, alkaline earth metal, ammonium, alkylsubstituted ammonium or mono-, di-, trialkanolammonium group with about1 to about 5 carbon atoms; R₁₁ is hydrogen (H), or an alkyl, alkenyl orhydroxyalkyl group having about 1 to about 5 carbon atoms; a and b areeach from about 0 to about 35 and the sum of a and b are from about 0 toabout 35; p and q are each from about 0 to about 3, r is from about 0 toabout 4, s is from about 0 to about 1 and the sum of p, q and r are fromabout 0 to about 6. Illustrative of this class include, but are notlimited to 3-amino-3-deoxymethylriboside, methylglucosidoamine(2-amino-2-deoxymethylglucoside), 2-amino-2odeoxymethylglucosidehydrochloride, 2-amino-2-deoxyethylglucoside,2-amino-2-deoxypropylglucoside, 2-amino-2-deoxyhydroxyethylglucoside,2-acetamido-2-deoxymethylglucoside, methylglucosidoamine-6-disulfate,methylglucosidoamine-6-phosphate, 3-amino-3-deoxyethylglucoside,4-amino-4-deoxybutylglucoside, 2-amino-2-deoxymethylmannoside,2-amino-2-deoxyhydroxyethylguloside,2-amino-2,6-dideoxyethylgalactoside,2-amino-2-deoxy-4-(2-amino-2-deoxy-β-glucopyranosyl)methylglucoside and2-amino-2-deoxy-4-O-(2-amino-2-deoxy-β-glucopyranosyl)₄ methylglucoside.

Still other examples of glycamines (6-amino-6-deoxyaldoses,6-amino-6-deoxyketoses, 6-amino-6-deoxyglycosides etc.) suitable forthis method include those of the formula: ##STR37## wherein G ishydrogen (H), a (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) H group, a mono-,di-, oligo- or polysaccharide or mixtures thereof; R₁₂ is hydrogen (H),or an alkyl, alkenyl or hydroxyalkyl group having about 1 to about 5carbon atoms; a and b are each from about 0 to about 35 and the sum of aand b are from about 0 to about 35; o is from about 0 to about 2, p isfrom about 0 to about 4 and q is from about 0 to about 3. Illustrativeof this class include, but are not limited to 5-amino-5-deoxyribose,5-amino-5-deoxy-xylose, 6-amino-6-deoxyallose, 6-amino-6-deoxyaltrose,6-amino-6-deoxyglucose, 6-amino-6-deoxyglucose hydrochloride,6-amino-6-deoxymethylglucoside, 6-amino-6-deoxyethylglucoside,6-amino-6-deoxymannose, 6-amino-6-deoxygulose, 6-amino-6-deoxyidose,6-amino-6-deoxygalactose, 6-amino-6-deoxytalose,7-amino-7-deoxyglucoheptose, 7-amino-7-deoxy-glyceroglucoheptose,7-amino-7-deoxyglycergalactoheptose, 7-amino-7-deoxyglyceromannoheptose,6-amino-6-deoxyfructose, 7-amino-7-deoxyalloheptulose,7-amino-7-deoxymannoheptulose, 7-amino-7-deoxysedo-heptulose,7-amino-7-deoxytaloheptulose, 8-amino-8-deoxyglycerogalactooctulose,8-amino-8-deoxyglyceromannooctulose,9-amino-9-deoxyerythrogalactononulose,9-amino-9-deoxyerythroglucononulose,galactopyranosyl-β-(1-4)-6-amino-6-deoxyglucose,6-amino-6-deoxygalactose-β-(1-4)-glucopyranose,6-amino-6-deoxygalactose-β-(1-4)-6-amino-6-deoxyglucose,glucopyranosyl-α-(1-4)-6-amino-6-deoxyglucose,6-amino-6-deoxyglucose-α-(1-4)-glucopyranose, 1-amino-1-deoxy-β-fructofuranosyl-α-glucopyranoside,6-amino-6-deoxy-β-fructofuranosyl-α-glucopyranoside,β-fructofuranosyl-α-6-amino-6-deoxyglucopyranoside andglucopyranosyl-α-(1-4)-{glucopyranosyl-α-(1-4)}₅-6-amino-6-deoxyglucose.

Yet other examples of glycamines suitable for this method include theZ-amino-Z-deoxyketoses wherein Z is from about 2 to about 8.Illustrative of this class include, but are not limited5-amino-5-deoxyxylohexulose and 6-amino-6-deoxyxylohexulose.

Many additional examples of glycamines that are useful in the presentinvention are described in "Carbohydrates" edited by Collins, publishedby Chapman and Hall Ltd., (1987) and "The Carbohydrates, Chemistry andBiochemistry" edited by Pigman and Horton, 2nd Edition, Volumes IA, IIA,IB and lIB, published by Academic Press Inc., (1972); all of which areincorporated herein by reference.

Of the above described glycamines, those of the following formulas aremost highly preferred: ##STR38## wherein G is hydrogen (H) or amonosaccharide; R12 is hydrogen (H) or an alkyl, alkenyl or hydroxyalkylgroup having from about 1 to about 4 carbon atoms; m=0; n=1-4; o=0-1;p=0-1 and q=1.

Examples of suitable alkenyl succinic anhydrides, which are prepared bythe condensation of maleic anhydride with an alkene (olefin), that areuseful in the present method include, but are not limited tooctenylsuccinic anhydride, diisobutylenesuccinic anhydride,nonenylsuccinic anhydride, decenylsuccinic anhydride, undecenylsuccinicanhydride, dodecenylsuccinic anhydride, triisobutylenesuccinicanhydride, tridecenylsuccinic anhydride, tetradecenylsuccinic anhydride,pentadecenylsuccinic anhydride, hexadecenylsuccinic anhydride,tetraisobutylenesuccinic anhydride, heptadecenylsuccinic anhydride,octadecenylsuccinic anhydride and mixtures thereof.

Examples of suitable alkyl succinic anhydrides, which are prepared byhydrogenating alkenyl succinic anhydrides, that are useful in thepresent method include, but are not limited to octylsuccinic anhydride,nonyl- succinic anhydride, decylsuccinic anhydride, undecylsuccinicanhydride, dodecylsuccinic anhydride, tridecylsuccinic anhydride,tetradecylsuccinic anhydride, pentadecylsuccinic anhydride,hexadecylsuccinic anhydride, heptadecylsuccinic anhydride,octadecylsuccinic anhydride, isodecylsuccinic anhydride,isododecylsuccinic anhydride, isotridecylsuccinic anhydride,isotetradecylsuccinic anhydride, octyloxysuccinic anhydride,nonyloxysuccinic anhydride, decyloxysuccinic anhydride,undecyloxysuccinic anhydride, dodecyloxysuccinic anhydride,dodecyloxy(dioxyethylene)succinic anhydride,dodecyloxy(trioxyethylene)succinic anhydride,tetradecyloxy(tetraoxyethylene)succinic anhydride,tetradecyloxy(hexaoxyethylene)succinic anhydride,tetradecyloxy(pentaoxypropylene)succinic anhydride,dodecyloxy(dioxyethylenetrioxypropylene)succinic anhyd-ride as well asC₈ -C₁₈ alkyl hydroxysuccinic anhydride, C₈ -C₁₈ alkyl hydroxysulfonatesuccinic anhydride, C₈ -C₁₈ alkyl epoxysuccinic anhydride, C₈-C₁₈ alkyl dichlorosuccinic anhydride, C₈ -C₁₈ alkyl sulfonatesuccinicanhydride, adipic anhydride and mixtures thereof.

The alkyl- and alkenyl succinic acids (dicarboxylic acids), which areprepared by the condensation of maleic acid or fumaric acid with analkene or by hydrolysis of an alkylo or alkenyl succinic anhydride, areuseful as well however, the methyl, ethyl, propyl, isopropanol, butyl,hexyl esters and the like of alkyl- and alkenyl succinic acids arepreferred, since products obtained from these materials are isolated ongood yield and color.

Other examples of alkyl- and alkenyl dicarboxylic acids useful in thepresent method include those obtained by the condensation of itaconicacid, citraconic acid, mesaconic acid, trans-glutaconic acid,trans-β-hydromuconic acid, aconitic acid and the like with an alkene.Specific examples include, but are not limited to2-octenyl-2-methylsuccinic acid, 2-decenyl-2-methylsuccinic acid,2-decyl-2-methylsuccinic acid, 2-dodecenyl-2-methylsuccinic acid,2-tetradecenyl-2-methylsuccinic acid, 2-octenyl-3-methylsuccinic acid,2-decenyl-3-methylsuccinic acid, 2-dodecenyl-3-methylsuccinic acid,2-tetradecenyl-3-methylsuccinic acid, 2-octenylglutaric acid,2-decenylglutaric acid, 2-decylglutaric acid, 2-dodecenylglutaric acid,2-tetradecenylglutaric acid, 3-octenylglutaric acid, 3-decenylglutaricacid, 3-decylglutaric acid (3-decylpentan-1,5-dioic acid),3-dodecenylglutaric acid, 3-tetradecenylglutaric acid, 3-octenyladipicacid, 3-decenyladipic acid, 3-decyladipic acid, 3-dodecenyladipic acid,tetradecenyladipic acid, octylmalonic acid, decylmalonic acid,dodecylmalonic acid, tetradecylmalonic acid, dodecenylmalonic acid,2-octylsuberic acid, 4-butyldecan-1,10-dioic acid, and the like. Again,the methyl, ethyl, propyl, isopropanol, butyl or hexyl esters of thesealkyl- and alkenyl dicarboxylic acids are also preferred.

Methods for preparing alkyl- and alkenyl anhydrides, dicarboxylic acidsand the like are disclosed in U.S. Pat. Nos. 2,283,214 and 2,380,699 toKyrides et al. both of which are incorporated herein by reference. Ofthe above described hydrophobic substrates, the anhydrides are preferredfor use herein.

Within the process of the invention, it is desirable to use water-freereaction components, although small amounts of water (from about 1% toabout 15% by weight) can be tolerated.

Also, within the process of the invention, the glycamine can be addedprogressively to the anhydride, or the anhydride can be addedprogressively to the glycamine, preferably however, both reagents areadded in full amount at the beginning of the reaction. The glycamine canbe used in molar excess relative to the anhydride, or the anhydride canbe used in molar excess relative to the glycamine, preferably however,as seen in Examples 2 through 14, the reagents are used instoichiometric molar amounts.

The glycamine or the anhydride is preferably in crystalline to granularform, however solid, flake, paste, gel or liquid form can be used aswell.

The reaction may be performed at or below room temperature, howevershorter reaction times can be achieved at elevated temperature and isusually preferred. Favorable reaction temperatures are from about 30° C.to about 300° C., preferably from about 40° C. to about 250° C., mostpreferably from about 60° C. to about 200° C.

The reaction can be carried out under reduced pressure to assist in theremoval of water, however, it is preferably carried out at atmosphericpressure and under an inert gas blanket such as nitrogen, argon orhelium, most preferably it is carried out at atmospheric pressure.

Optionally a catalyst used to accelerate the rate of the reaction isgenerally classified as an organic or inorganic base. Examples ofsuitable base catalysts useful in the present method include, but arenot limited to sodium hydroxide, potassium hydroxide, ammoniumhydroxide, calcium hydroxide, magnesium hydroxide, sodium metal,potassium metal, sodium methoxide, potassium methoxide, sodium ethoxide,potassium ethoxide, sodium carbonate, potassium carbonate, ammoniumcarbonate, magnesium carbonate, calcium carbonate, lithium carbonate,sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate,magnesium bicarbonate, calcium bicarbonate, trisodium phosphate,tripotassium phosphate, tetrasodium pyrophosphate, tetrapotassiumpyrophosphate, pentasodium tripolyphosphate, pentapotassiumtripolyphosphate, disodium tartrate, dipotassium tartrate, sodiumpotassium tartrate, trisodium citrate, tripotassium citrate, sodiumacetate, potassium acetate, sodium valerate, sodium laurate, potassiumlaurate, sodium myristate, potassium myristate, sodium stearate, sodiumoleate, sodium 12-hydroxydodeconate, sodium 2,2-dimethylbutyrate,disodium oxalate, dipotassium oxalate, disodium malonate, dipotassiummalonate, disodium succinate, dipotassium succinate, disodium dodecylsuccinate, disodium glutarate, dipotassium glutarate, disodium1,12-dodecanedicarboxylate, trisodium tricarballylate, tripotassiumtricarballylate, tetrasodium 1,2,3,4-butanetetracarboxylate,tetrapotassium 1,2,3,4-butanetetracarboxylate, disodium itaconate,dipotassium itaconate, disodium maleate, dipotassium maleate, disodiumfumarate, dipotassium fumarate, disodium malate, disodium agaricate,dipotassium agaricate, sodium ethoxyacetate, sodium glyoxylate, sodium4-acetylbutyrate, sodium cyclohexylacetate, trisodium1,3,5-cyclohexanetricarboxylate, sodium basic silicates, potassium basicsilicates, sodium basic aluminosilicates, potassium basicaluminosilicates, sodium lactate, potassium lactate, ammonium lactate,sodium glycinate, sodium dimethylglycinate, pentasodiumdiethylenetriaminepentaacetate (DTPA), tetrasodiumethylenediaminetetraacetate (EDTA), tetrapotassiumethylenediaminetetraacetate, calcium disodiumethylenediaminetetraacetate, triethylamine, tripropylamine,tributylamine, trioctylamine, N,N-dimethyldodecylamine,N,N'-diethylethylenediamine, N,N-diethyl-N'-methylethylenediamine,N,N,N',N'-tetramethylethylenediamine,N,N,N',N'-tetraethylethylenediamine,N,N,N',N'-tetramethylethylenediamine,N,N,N',N'-tetraethyl-1,3-propanediamine, monoethanolamine,diethanolamine, triethanolamine, pyridine, morpholine, picoline,collidine, ethylpiperidine diethylcyclohexylamine and the like. Mixturesof base catalysts can be also used as well and may be preferred incertain cases. Preferred base catalysts include sodium hydroxide, sodiummethoxide, sodium carbonate, potassium carbonate, sodium bicarbonate,trisodium citrate, sodium laurate, disodium oxalate, triethylamin,tripropylamine, monoethanolamine, diethanolamine, triethanolamine andmixtures thereof.

The base catalyst can be added at any time during the reaction, however,it is preferably added at the beginning of the reaction and in fullamount. The molar ratio of glycamine to base catalyst is from about500:1 to about 1:1, preferably from about 250:1 to about 5:1, mostpreferably from about 150:1 to about 10:1.

The substrates are reacted with intensive stirring for several hours,preferably from about 0.5 hour to about 20 hours, more preferably fromabout 1 hour to about 15 hours, most preferably when the water ofreaction is completely removed and is verified by an analyticaltechnique such as thin layer chromatography (TLC), infrared spectroscopy(IR), proton nuclear magnet resonance (H1 NMR), carbon 13 nuclear magnetresonance (C13 NMR), direct chemical ionization mass spectrometry (DCIMS), fast atom bombardment mass spectrometry (FAB MS), or high pressureliquid chromatography (HPLC).

In general, water or an organic solvent can be used to perform thereaction of the present invention, however, these materials are notnecessary and are therefore not preferred. However, when an organicsolvent is used, the quantity of solvent should be sufficient todissolve the carbohydrate and anhydride, but otherwise this is not anessential condition. An organic solvent may become neccessary when heatsensitive carbohydrates are used (e.g., certain Z-deoxy-Z-aminoaldosesor ketoses). Typical levels of solvent used are from about 5% to about95%, preferably from about 15% to about 75%, most preferably from about30% to about 50% by weight of the total reaction mixture. Preferably thesolvent is removed (after the reaction is complete) by known proceduressuch as simple distillation, vacuum distillation or rotaevaporation.When water is used, it may be removed by freeze drying, spray drying, orvacuum distillation, however, it may be more economical to leave thewater in and use it as a diluent making the product a pureable liquid.Typical levels of water used as a reaction solvent or diluent are fromabout 5% to about 95%, preferably from about 15% to about 65%, mostpreferably from about 25% to about 50% by weight of the total reactionmixture.

In general, the nonionic alkyl- and alkenyl glycasuccinimide surfactantsof the present invention are usually isolated as solids, however, whensyrups are obtained, crystallization may be enhanced by the addition ofan organic solvent. The resulting product is subsequently filtered,washed with an organic solvent and air or vacuum dried.

Optionally, further purification of (solid) alkyl- and alkenylglycasuccinimide surfactants can be performed by recrystallization in anorganic solvent. The amount of solvent used is sufficient to dissolvethe product, preferably with heating. The solution is then slowly cooleduntil recrystallization is complete, subsequently filtered, washed withan organic solvent and air or vacuum dried.

Typical reaction solvents, crystallization solvents andrecrystallization solvents that may be used include, but are not limitedto acetic acid, acetone, acetonitrile, butanol, sec-butanol,tert-butanol, butylacetate, butyl chloride, chloroform, cyclohexane,cyclopentane, dimethylformaide (DMF), dimethylacetamide,dimethylsulfoxide (DMSO), 2-ethoxyethanol, ethylacetate, ethyl ether,ethylene glycol dimethyl ether (glyme), penlane, hexane, heptane,hexadecane, methanol, 2-methoxyethanol, 2-methoxyethyl acetate,methylethylketone (MEK), methylisoamylketone, methylisobutylketone,butylmethylketone, diisobutylketone, N-methyl-2-pyrrolidine, petroleumether, propanol, isopropanol, propylene carbonate, pyridine,tetrachloroethylene, tetrahydrofuran (THF), tetramethylurea, toluene,trichloroethylene, 1,2,2-trichloro-1,2,2-trifluoroethane,2,2,4-trimethylpenlane, xylene, ethanol, pentylacetate, carbondisulfide, 1-chlorobutane, 1,2-dichloroethane, 1,2-dimethoxyethane,glycerol, methylcyclohexane, ethylene glycol, furan,1,2-dimethoxyethane, propylene glycol, 1-chloro-1,1-difluoroethane,isopropylbenzene (cumene), cyclohexanol, cyclohexanone,4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), diethylene glycol,diisopropyl ether, ethylene glycol monobutyl ether (2-butoxyethanol),ethylene glycol monomethyl ether (2-methoxyethanol), hexylene glycol,isopentylacetate, isobutylacetate, isopropylacetate, methylacetate,methylpentylketone, and the like, however, alcohols are the preferredreaction solvents and acetates or alcohols are the preferredrecrystallization solvents. Mixtures of solvents can be used as well andmay be preferred in certain cases.

When the reaction is complete, the catalyst may be optionallyneutralized with an organic or inorganic acid. Examples of suitableneutralizing acids include, but are not limited to hydrochloric acid,sulfuric acid, phosphoric acid, boric acid, nitric acid, oxalic acid,malonic acid, glutaric acid, adipic acid, sebacic acid, tricarballylicacid, 1,2,3,4-butanetetracarboxylic acid, itaconic acid, maleic acid,malic acid, fumaric acid, citraconic acid, glutaconic acid,bis(hydroxymethyl)propionic acid, tartaric acid, citric acid, formicacid, lactic acid, acetic acid, benzoic acid, gluconic acid,glucoheptonic acid, lactobionic acid, maltobionic acid, coconut fattyacid, lauric acid, myristic acid, palmitic acid, valeric acid,2-propylpentanoic acid, succinic acid, dodecenyl succinic acid, arotoniccrotonic acid, tiglic acid, glycolic acid, ketomalonic acid,methoxyacetic acid, ethoxyacetic acid, 3-methoxypropionic acid,6-nitrocaproic acid, levulinic acid, chelidonic acid,cyclobutanecarboxylic acid, 1,1-cyclohexanediacetic acid, glycine,phenylacetic acid, 3-benzoylpropionic acid, S-benzylthioglycolic acid,phenylmalonic acid, 2-hydroxyphenylacetic acid, toluenesulfonic acid,S-sulfobenzoic acid, 5-sulfoisophthalic acid, C₈ to C₁₈alkylbenzenesulfonic acid, methanesulfonic acid, ethanesulfonic acid,propanesulfonic acid, C₈ to C₁₈ alkyl sulfonic acid,3-hydroxy-1-propanesulfonic acid, isethionic acid, sulfur trioxide,anionic surfactants in the acid form, ion exchange resin and the like.Mixtures of acids can be used as well. Preferred neutralizing acidsinclude hydrochloric acid, oxalic acid, tartaric acid, citric acid,formic acid, lactic acid, lauric acid, dodecenyl succinic acid, C₈ toC₁₈ alkylbenzenesulfonic acid and methanesulfonic acid. The amount ofneutralizing acid used will be that which is sufficient to provide a pHin the range of about 4 to about 9, preferably from about 5 to about 8,most preferably about 7. Neutralization may be done in water or in aninert organic solvent or mixtures thereof, at about 0° C. to about 35°C.

Bleaching is sometimes required but not always necessary, sincecompounds of the invention are usually of good color. Bleaching agentsor peroxy compounds that may be used to further improve color arehydrogen peroxide, sodium hypochlorite, potassium hypochlorite, calciumhypochlorite, lithium hypochlorite, dibasic magenesium hypochlorite,sodium hypobromite, chlorinated trisodium phosphate, hypochlorous acid,chlorine dioxide, sodium percarbonate, potassium percarbonate, sodiumperborate monohydrate, sodium perborate tetrahydrate, oxone, t-butylhydroperoxide, benzoyl peroxide, bis(trimethylsilyl)peroxide,peroxymonosulfate, peroxyformic acid, peroxyacetic acid,peroxytrifluoroacetic acid, peroxybenzoic acid, m-chloroperoxybenzoicacid, peroxyphthalic acid, peroxymaleic acid, peroxypropionic acid,peroxylauric acid and the like. However, hydrogen peroxide and hydrogenperoxide liberating or generating compounds are preferred. Bleaching maybe optionally done in water or in an inert organic solvent before orduring the reaction or after the reaction is complete, preferablyhowever, bleaching is done after the reaction is complete at about 0° C.to about 50° C. and in water or an organic solvent. Typical levels ofbleaching agent are from about 0.01% to about 10%, preferably from about0.02% to about 7%, even more preferably from about 0.03% to about 5% byweight of the total reaction mixture.

Color improvement may also be carried out by using reducing agentsbelonging to two classes.

The first class of agents comprises compounds which include sulfur inthe +4 oxidation state and show a negative oxidation relative tohydrogen. Illustrative of this class are salts of sulfite, bisulfite,hydrosulfite (dithionite), metabisulfate (pyrosulfite) and mixturesthereof. Suitable salt counter ions include alkali metal, alkaline earthmetal, ammonium, alkyl- or hydroxyalkylammonium cations and mixturesthereof. Specific examples include, but are not limited to sodiumsulfite, potassium sulfite, calcium sulfite, sodium bisulfite (sodiumhydrogen sulfite), potassium bisulfite, sodium hydrosulfite, zinchydrosulfite, sodium metabisulfite and potassium metabisulfite. Sulfurdioxide, sulfurous acid and sodium sulfoxylate formaldehyde are usefulas well.

The second class of reducing agents includes those compounds havinghydrogen in the -1 oxidation state and show a negative oxidationpotential relative to hydrogen. Illustrative of this class are sodiumhydride, potassium hydride, calcium hydride, lithium hydride, magnesiumhydride, sodium borohydride, sodium cyano borohydride potassiumborohydride, lithium borohydride, magenesium borohydride, alkyl- andalkoxy borohydrides, aluminum hydride, sodium aluminum hydride,potassium aluminum hydride, calcium aluminium hydride, lithium aluminumhydride, alkyl- and alkoxy aluminum hydrides such as sodiumdihydrobis(2-methoxyethoxy)aluminate, diboranes and mixtures thereof.Particularly preferred among the foregoing are the bisulfites andborohydrides, most especially preferred are sodium bisulfite and sodiumborohydride and mixtures thereof. Reduction may be optionally done inwater or in an inert organic solvent before or during the reaction orafter the reaction is complete, preferably however, reduction is donewithout water or an organic solvent and after the reaction is completeat about 0° C. to about 200° C. Typical levels of reducing agent arefrom about 0.01% to about 12%, preferably from about 0.02% to about 9%,even more preferably from about 0.03% to about 7% by weight of the totalreaction mixture.

In the third embodiment of the invention, a similar class of nonionicglyeasuccinamide surfactant is described, specifically alkyl- andalkenyl bis(glyca)succinamides.

An alkyl- or alkenyl bis(glyca)succinamide is defined as an alkyl- oralkenyl amide of an 1-amino-1-deoxyalditol, 1-amino-1,6-dideoxyalditolor 2-amino-2-deoxyketitol, which in turn, is defined as a sugarsubstance in which the pseudoaldehyde or pseudoketose group, generallyfound at the C₁ or C₂ position of the sugar, has been reduced to anamino group through a reductive amination reaction with ammonia andhydrogen in the presence of a metal catalyst such as nickel. Thereaction is typically done in water or organic solvent, but is usuallydone in a mixture of both. Methods of preparing such glycamines are wellknown in the art and are described in the J. Chem. Soc. 1682, (1922) toLing et al.; J. Amer. Chem. Soc. 62, 3315, (1940) to Wayne et al., 72,5416, (1950) to Holly et al., 79, 3541, (1957) to Kagan et al.; Methodsin Carbohydr. Chem. 2, 79, (1963) to Long et al.; U.S. Pat. Nos.2,016,962 to Flint et al., 2,621,175 to Holly et al.; and EP ApplicationNo. 0,536,939 to Beck all of which are incorporated herein by reference.

An alkyl- or alkenyl bis(glyca)succinamide can also be defined as analkyl- or alkenyl amide of an 1-alkylamino-1-deoxyalditol,1-alkylamino-1,6-dideoxyalditol or 2-alkylamino-2-deoxyketitol, which inturn, is defined as a sugar substance in which the pseudoaldehyde orpseudoketose group, generally found at the C₁ or C₂ position of thesugar, has been reduced to an alkylamino group through a reductiveamination reaction with an C₁ -C₂₈ alkylamine and hydrogen in thepresence of a metal catalyst such as nickel. The reaction is typicallydone in water or organic solvent, but is preferably done in a mixture ofboth. Methods of preparing such glycamines are well known in the art andare described in U.S. Pat. No. 5,334,764 to Scheibel et al., U.S. Pat.No. 2,016,962 to Flint et al., d. Amer. Chem. Soc. 66, 483 (1944) and J.Dispersion Science and Technology 12 (3&4), 227, (1991) all of which areincorporated herein by reference.

An alkyl- or alkenyl bis(glyca)succinimide can be further defined as analkyl- or alkenyl amide of a Z-amino-Z-deoxyalditol (hydrogenatedaldosamine or ketosamine), wherein Z is from about 2 to about 8, whichin turn, is defined as a sugar substance in which the pseudoaldehyde orpseudoketose group, generally found at the C₁ or C₂ position of thesugar, has been reduced to a hydroxyl group with hydrogen in thepresence of a metal catalyst such as nickel or platinum or a metalreducing agent such as sodium borohydride. The reaction is typicallydone in water. Methods of preparing such glycamines are well known inthe art and are described in the J. Biol. Chem. 120, 577, (1937) toLevene et al.; Helv. Chim. Acta. 20, 627, (1937) to Karrer et al.; Chem.Ber. 102, 459, (1969) to Paulsen et al.; and U.S. Pat. No. 4,307,072 toSmith all of which are incorporated herein by reference.

An alkyl- or alkenyl bis(glyca)succinamide can be even further definedas an alkyl- or alkenyl amide of a Z-amino-Z-deoxyaldose,Z-amino-Z-deoxy-ketose, Z-amino-Z-deoxyglycoside,Z-alkylamino-Z-deoxyaldose, Z-alkyl-amino-Z-deoxyketose,Z-alkylamino-Z-deoxyglycoside, wherein Z is from about 1 to about 8.Methods of preparing or isolating such glycamines are well known in theart and are described in Adv. Carbohydr. Chem. 7, 47, (1957) to Fosteret al., 13, 189, (1958) to deanloz,; Methods in Carbohydr. Chem. 1,228,(1962) to Stacey et al.; Chem. Ber. 103, 1599, (1970) to Paulsen et al.;Can. ,1. Chem. 46, 1586, (1968) to Sowa et al.; J. Am. Chem. Soc. 81,3716, (1959) to Wolfrom et al.; Helv. Chim. Acta 46, 282, (1963) toHardegger et al., 40, 342, (1957) to Druey et al.; Ann. 148, 600, (1956)to Kuhn et al,; and J. Org. Chem. 26, 603, (1961) to Zaugg all of whichare incorporated herein by reference.

A bis(glyca)succinamide may be based on carbohydrates comprising onesaccharide unit [e.g., bis(ribo)succinamides, bis(gluco)succinamides,bis(2-deoxy-2-aminosorbitol)succinamides, bis(glucohepto)succinamides orbis(fructo)succinamides], two saccharide units [e.g.,bis(lacto)succinamides, bis(malto)succinamides orbis(cellobio)succinamides], three saccharide units [e.g.,bis(maltotrio)succinamides or bis(cellotrio)succinamides] or they may bebased on compounds comprising more than three saccharide units [e.g.,bis(maltohepto)succinamides]. It should be noted that any carbohydratecan be used as long as the sugar has an amino group or a pseudoaldehydeor pseudoketose group available for reduction to an amino group.

In general, the nonionic alkyl- and alkenyl bis(glyca)succinamidesurfactants are of the formula: ##STR39## wherein:

A₂ represents the following structures which are attached to thesuccinate ring via the nitrogen (N) atom; ##STR40##

A₁ is A₂, OR₁₂, O(CH₂ CH₂ O)_(a) R₉, O(CH₂ CHCH₃ O)_(b) R₁₀, N(R₁₂)₂,NH[(CH-X)_(d) Y]_(e) R₉ group or mixtures thereof;

R₁₃ is hydrogen (H), a straight or branched chain saturated orunsaturated hydrocarbon which may be unsubstituted or substituted with ahydroxyl, polyhydroxyl, aromatic, cycloaliphatic or mixed aromaticradical having about I to about 31 carbon atoms;

G, M, W, X, Y, Z, R₉, R₁₀, R₁₁, R₁₂, a, b, c, d, e, m, n, o, p, q, r,and s are the same as defined for formula (I) above.

More preferably:

A₂ represents the following structures which are attached to thesuccinate ring via the nitrogen (N) atom; ##STR41##

A₁ is A₂, OR₁₂, N(R₁₂)₂ group or mixtures thereof;

G is hydrogen (H), a (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) H group, amonosaccharide or mixtures thereof;

X is hydrogen (H), an alkyl group having about 1 to about 2 carbon atomsor mixtures thereof;

Y is an oxygen atom (O);

Z is a CH═CH, CH₂ CH₂ group or mixtures thereof;

R₉ is a straight or branched chain saturated hydrocarbon radical havingabout 3 to about 23 carbon atoms;

R₁₂ is hydrogen (H), an alkyl, alkenyl or hydroxyalkyl group havingabout 1 to about 4 carbon atoms or mixtures thereof;

R₁₃ is hydrogen (H), a straight or branched chain saturated orunsaturated hydrocarbon which may be unsubstituted or substituted with ahydroxyl, polyhydroxyl radical having about 1 to about 6 carbon atoms;

a=0-15;

b=0-15;

c=1-2;

d=1-4;

e=0-15;

m=0-5;

n=1-5;

o=0-1;

p=0-2;

and q=0-2.

A specific example of a monosaccharide alkyl bis(glyca)succinamidecompound of the invention is dodecyloxy bis(D-gluco)succinamide havingthe formula: ##STR42## wherein based on formula (II) above: ##STR43##G=hydrogen (H); R₉ =C₁₀ H₂₁ ;

R₁₃ =hydrogen (H);

W=oxygen (O);

Z=CH₂ CH₂ ;

c=1;

e=0;

m=0;

and n=4.

Another specific example of a monosaccharide alkyl bis(glyca)succinamidecompound of the invention is tetradecyloxytri(oxyethyl) bis(D-gluco)succinamide, also known as tetradecyloxy(triethylene glycol)ether bis(D-gluco)succinamide or as tetradecyloxy(trioxyethylene)bis(D-gluco)succinamide having the formula: ##STR44## wherein based onformula (II) above: ##STR45## G=hydrogen (H); R₉ =C₁₂ H₂₅ ;

R₁₃ =hydrogen (H);

W=oxygen (O);

X=hydrogen (H);

Y=oxygen (O);

Z=CH₂ CH₂ ;

c=1;

d=2;

e=3;

m=0;

and n=4.

Yet another specific example of a monosaccharide alkylbis(glyca)succinamide compound of the invention is dodecylbis(D-gluco)succinamide hexaoxyethylene ether, also known as dodecylbis(D-gluco)succinamide hexaethylene glycol ether or more generally aspolyoxyethylene (6) dodecyl bis(D-gluco)succinamide having the formula:##STR46## wherein based on formula (II) above: ##STR47## G=hydrogen (H)or (CH₂ CH₂ O)_(a) H group; R₉ =C₉ H₁₉ ;

R₁₃ =hydrogen (H);

W=CH₂ ;

Z=CH₂ CH₂ ;

a=can vary from about 1 to about 12 for a total average of 6;

c=1;

e=0;

m=0;

and n=4.

A specific example of a monosaccharide alkenyl bis(glyca)succinamidecompound of the invention is decenyl bis(D-gluco)succinamide also knownas decenyl bis(1-amido-1-deoxy D-glucitol) succinate or decenylbis(1-amido-1-deoxy D-sorbitol) succinate having the formula: ##STR48##wherein based on formula (II) above: ##STR49## G=hydrogen (H); R₉ =C₇H₁₅ ;

R₁₃ =hydrogen (H);

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

and n =4.

Another specific example of a monosaccharide alkenylbis(glyca)succinamide compound of the invention is dodecenylbis(L-rhamno)succinamide also known as dodecenyl bis(1-amido-1,6-dideoxyL-rhamnitol) succinate or dodecenyl bis(1-amido-1,6-dideoxy L-mannitol)succinate having the formula: ##STR50## wherein based on formula (II)above: ##STR51## G=hydrogen (H); R₉ =C₉ H₁₉ ;

R₁₃ =hydrogen (H);

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

and n=4.

A specific example of a cyclic monosaccharide alkenylbis(glyca)succinamide compound of the invention is decenylbis(D-sorbitan)succinamide having the formula: ##STR52## wherein basedon formula (II) above: ##STR53## G=hydrogen (H); R₉ =C₇ H₁₅ ;

R₁₃ =hydrogen (H);

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

p=1;

and q=1.

Another specific example of a cyclic monosaccharide alkenylbis(glyca)succinamide compound of the invention is dodecenylbis(1-amido-1 -deoxy D-fructopyranosyl) succinate having the formula:##STR54## wherein based on formula (II) above: ##STR55## G=hydrogen (H);R₉ =C₉ H₁₉ ;

R₁₃ =hydrogen (H);

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

o=1;

and p=0.

Yet another specific example of a cyclic monosaccharide alkenylbis(glyca)succinimide compound of the invention is dodecenylbis(6-amido-6-deoxy α,β-D-methylglucopyranoside) succinate having theformula: ##STR56## wherein based on formula (IX) above: ##STR57##G=hydrogen (H); R₉ =C₉ H₁₉ ;

R₁₂ =CH₃ ;

R₁₃ =hydrogen (H);

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

o=1;

and p=1.

A specific example of a monosaccharide alkyl bis(alkylglyca)succinamidecompound of the invention is tetradecyloxydi(oxyethyl) bis(methylD-gluco)succinamide, also known as tetradecyloxy(diethylene glycol)ether bis(methyl D-gluco)succinamide or as tetradecyloxy(dioxyethylene)bis(methyl D-gluco)succinamide having the formula: ##STR58## whereinbased on formula (II) above: ##STR59## G=hydrogen (H); R₉ =C₁₂ H₂₅ ;

R₁₃ =CH₃ ;

W=oxygen (O);

X=hydrogen (H);

Y=oxygen (O);

Z=CH₂ CH₂ ;

c=1;

d=2;

e=2;

m=0;

and n=4.

Another specific example of a monosaccharide alkylbis(alkylglyca)succinamide compound of the invention is tetradecylbis(methyl D-gluco)succinamide having the formula: ##STR60## whereinbased on formula (II) above: ##STR61## G=hydrogen R₉ =C₁₃ H₂₉ ;

R₁₃ =CH₃ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

and n=4.

A specific example of a monosaccharide alkenylbis(alkylglyca)succinamide compound of the invention is hexadecenylbis(methyl D-gluco)succinamide having the formula: ##STR62## whereinbased on formula (II) above: ##STR63## G=hydrogen (H); R₉ =C₁₁ H₂₃ ;

R₁₃ =CH₃ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

and n=4.

A specific example of a mixed monosaccharide alkenylbis(alkylglyca)succinamide compound of the invention is dodecenyl methylD-sorbitan(methyl D-gluco)succinamide having the formula: ##STR64##wherein based on formula (II) above: ##STR65## G=hydrogen (H); R_(9=C) ₉H₁₉ ;

R₁₃ =CH₃ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

n=4;

p=1;

and q=1:

A specific example of a mixed monosaccharide alkenylalkylglycasuccinamide compound of the invention is decenyl methylD-glucamidemethylsuccinate having the formula: ##STR66## wherein basedon formula (II) above: ##STR67## A₁ =OCH₃ G=hydrogen (H);

R₉ =C₇ H₁₅ ;

R₁₃ =CH₃ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

and n=4.

Yet another specific example of a mixed monosaccharide alkenylalkylglycasuccinamide compound of the invention is tetradecenylethanolamide(ethylgluco)succinamide having the formula: ##STR68##wherein based on formula (II) above: ##STR69## A₁ =NHCH₂ CH₂ OHG=hydrogen (H);

R₉ =C₁₁ H₂₃ ;

R₁₃ =CH₂ CH₃ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

and n=4.

Yet another specific example of a mixed monosaccharide alkenylalkylglycasuccinamide compound of the invention is hexadecenyldiglucamide methylsuccinate also known as hexadecenyl disorbitylamidemethylsuccinate having the formula: ##STR70## wherein based on formula(II) above: ##STR71## A₁ =OCH₃ G=hydrogen (H);

R₉ =C₁₃ H₂₇ ;

R₁₃ 32 sorbityl;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

and n=4.

A specific example of a mixed monosaccharide alkyl alkylglycasuccinamidecompound of the invention is hexadecenylethanolamide-(hydroxylethylgluco)succinamide having the formula:##STR72## wherein based on formula (II) above: ##STR73## A₁ =NHCH₂ CH₂OH G=hydrogen (H);

R₉ =C₁₃ H₂₇ ;

R₁₃ =CH₂ CH₂ OH

W=CH₂ ;

Z=CH₂ CH₂ ;

C=1;

e=0;

m=0;

and n=4.

A specific example of a disaccharide alkyl bis(glyca)succinamidecompound of the invention is tetradecyl bis(D-lacto)succinamide havingthe formula: ##STR74## wherein based on formula (II) above: ##STR75##G=hydrogen (H) or galactose; R₉ =C₁₁ H₂₃ ;

R₁₃ =hydrogen (H);

W=CH₂ ;

Z=CH₂ CH₂ ;

c=1;

e=0;

m=0;

and n=4.

A specific example of a disaccharide alkenyl bis(alkylglyca)succinamidecompound of the invention is hexadecenyl bis(methyl D-lacto)succinamidehaving the formula: ##STR76## wherein based on formula (II) above:##STR77## G=hydrogen (H) or galactose; R₉ =C₁₃ H₂₇ ;

R₁₃ =CH₃ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

and n=4.

A specific example of a mixed disaccharide/monosaccharide alkenylbis(alkylglyca)succinamide compound of the invention is tetradecenylmethyl D-malto(methyl D-gluco)succinamide having the formula: ##STR78##wherein based on formula (II) above: ##STR79## G=hydrogen (H) orglucose; R₉ =C₁₁ H₂₃ ;

R₁₃ =CH₃ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

and n=4.

Yet another specific example of a mixed disaccharide/monosaccharidealkenyl bis(alkylglyca)succinamide compound of the invention isdodecenyl methyl D-malto(methyl D-sorbitan)succinamide having theformula: ##STR80## wherein based on formula (II) above: ##STR81##G=hydrogen (H) or glucose: R₉ =C₉ H₁₉ ;

R₁₃ =CH₃ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

n=4.

p=1;

and q=1.

A specific example of a mixed disaccharide alkenyl alkylglycasuccinamidecompound of the invention is dodecenyl methyl D-maltamidemethylsuccinate having the formula: ##STR82## wherein based on formula(II) above: ##STR83## A₁ =OCH₃ G=hydrogen (H) or glucose;

R₉ =C₉ H₁₉ ;

R₁₃ =CH₃ ;

W=CH₂ ;

Z=CH═CH;

c=1;

e=0;

m=0;

and n=4.

Other examples of compounds of the invention are set forth below:

alkyl and alkenyl bis(D-erythro)succinamide

alkyl and alkenyl bis(D-threo)succinamide

alkyl and alkenyl bis (D-ribo)succinamide

alkyl and alkenyl bis(D-arabino)succinamide

alkyl and alkenyl bis(D-xylo)succinamide

alkyl and alkenyl bis(D-lyxo)succinamide

alkyl and alkenyl bis(D-allo)succinamide

alkyl and alkenyl bis(D-altro)succinamide

alkyl and alkenyl bis(D-ido)succinamide

alkyl and alkenyl bis(D-talo)succinamide

alkyl and alkenyl bis(D-gluco)succinamide

alkyl and alkenyl bis(L-gluco)succinamide

alkyl and alkenyl bis(D-galacto)succinamide

alkyl and alkenyl bis(L-galacto)succinamide

alkyl and alkenyl bis(D-manno)succinamide

alkyl and alkenyl bis(D-gulo)succinamide

alkyl and alkenyl bis(D-fructo)succinamide

alkyl and alkenyl bis(L-fructo)succinamide

alkyl and alkenyl bis(D-sorbo)succinamide

alkyl and alkenyl bis(L-sorbo)succinamide

alkyl and alkenyl bis(D-isomalto)succinamide

alkyl and alkenyl bis(D-isomalt)succinamide

alkyl and alkenyl bis(D-isomaltulo)succinamide

alkyl and alkenyl bis(D-trehalulo)succinamide

alkyl and alkenyl bis(D-ribulo)succinamide

alkyl and alkenyl bis(D-xylulo)succinamide

alkyl and alkenyl bis(D-3-ketosucro)succinamide

alkyl and alkenyl bis(D-leucro)succinamide

alkyl and alkenyl bis(D-lactulo)succinamide

alkyl and alkenyl bis(D-psico)succinamide

alkyl and alkenyl bis(D-rhamno)succinamide

alkyl and alkenyl bis(D-malto)succinamide

alkyl and alkenyl bis(L-malto)succinamide

alkyl and alkenyl bis(D-lacto)succinamide

alkyl and alkenyl bis(L-lacto)succinamide

alkyl and alkenyl bis(D-melibio)succinamide

alkyl and alkenyl bis(D-cellobio)succinamide

alkyl and alkenyl bis(D-cellulo)succinamide

alkyl and alkenyl bis(D-dextro)succinamide

alkyl and alkenyl bis(D-gluco)succinamide monooxyethylene ether

alkyl and alkenyl bis(D-gluco)succinamide dioxyethylene ether

alkyl and alkenyl bis(D-gluco)succinamide trioxyethylene ether

alkyl and alkenyl bis(D-gluco)succinamide pentaoxyethylene ether

alkyl and alkenyl bis(D-gluco)succinamide hexaoxyethylene ether

alkyl and alkenyl bis(D-gluco)succinamide octaoxyethylene ether

alkyl and alkenyl bis(D-gluco)succinamide nonaoxyethylene ether

alkyl and alkenyl bis(D-gluco)succinamide decaoxyethylene ether

alkyl and alkenyl bis(D-gluco)succinamide trioxypropylene ether

alkyloxy(monooxyethylene) bis(D-gluco)succinamide

alkyloxy(dioxyethylene) bis(D-gluco)succinamide

alkyloxy(trioxyethylene) bis(D-gluco)succinamide

alkyloxy(pentaoxyethylene) bis(D-gluco)succinamide

alkyloxy(heptaoxyethylene) bis(D-gluco)succinamide

alkyloxy(decaoxyethylene) bis(D-gluco)succinamide

alkyloxy(pentaoxypropylene) bis(D-gluco)succinamide

alkyloxyethylamino bis(D-gluco)succinamide

alkyloxyethylamido bis(D-gluco)succinamide

Wherein the alkyl or alkenyl group contains from about 1 to about 31carbon atoms; preferably from about 2 to about 25 carbon atoms, evenmore preferably from about 3 to about 23 carbon atoms.

If the R₁₃ group is an aliphatic radical (saturated or unsaturatedhydrocarbon), suitable examples include methyl, ethyl, propyl, butyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, coco, soya,tallow, tall oil, castor, corn, cottonseed, palm, rapeseed, safflower,sesame, sunflower, fish oil, allyl, octenyl, nonenyl, decenyl,undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl,hexadecenyl, hepta-decenyl, octadecenyl (oleyl), linoleyl and linolenyl.

If the R₁₃ group is interrupted by an aromatic group, the aromaticradical may be for example, benzyl or aniline. Cycloaliphatic radicalsare exemplified, but not limited to cyclopentyl and cyclohexyl. Suitablemixed aromatic aliphatic radicals are exemplified by benzylpropyl,phenylethyl, phenoxyethyl and vinylbenzyl.

The alkyl- and alkenyl D-bis(glyca)succinamide compounds of the presentinvention can also be ethoxylated, propoxylated or butoxylated withethylene oxide, propylene oxide, butylene oxide or mixtures thereof togive a series of novel polyoxyalkylene sugar surfactants.

The alkyl- and alkenyl D-bis(glyca)succinamide compounds of the presentinvention can also be sulfated with chlorosulfonic acid, sulfurtrioxide, sulfur trioxide/Lewis base complexes, oleum, sulfuric acid,sulfamic acid and the like as well as mixtures thereof, to give a seriesof novel sulfated sugar based anionic surfactants.

The alkyl- and alkenyl D-bis(glyca)succinamide compounds of the presentinvention can also be phosphorylated with phophorus oxychloride,phosphorous pentoxide, polyphosphoric acid, phosphoric acid, phosphorustrichloride and the like as well as mixtures thereof, to give a seriesof novel phosphated sugar based esters (mono-, di-, and triesters aswell as mixtures thereoff as anionic surfactants.

In a forth embodiment of the invention, a new and improved process forthe manufacture of alkyl- and alkenyl bis(glyca)succinamide surfactantsis described.

It has been found, in accordance with the present invention, that novelalkyl- and alkenyl bis(glyca)succinamide surfactants may be readilyprepared by (Step IB) reacting alkyl- or alkenyl succinic anhydrideswith alcohols in the presence of an acid catalyst at elevatedtemperatures (Δ) to give the corresponding alkyl- or alkenyl succinatewhich is then (Step IIC) reacted with glycamines (sugar-NHR₁₃) in thepresence of a base catalyst at elevated temperatures (Δ). The inventioncan be more readily understood when reference is made to the followinggeneral equations (B and C): ##STR84##

The method is suitable for the manufacture of alkyl- and alkenylbis(glyca)succinamide compounds wherein W is preferably CH₂ or an oxygenatom (O); X is preferably hydrogen (H), or an alkyl group having about 1to about 2 carbon atoms; Y is preferably a NR₁₀, +N(R₁₀)₂, oxygen (O)group or mixtures thereof; Z is preferably a CH═CH or CH₂ CH₂ group; R₉is preferably a straight chain saturated hydrocarbon which may beunsubstituted or substituted with an aromatic, cycloaliphatic or mixedaromatic radical comprising from about 2 to about 25 carbon atoms; R₁₃is preferably hydrogen (H), a straight or branched chain saturated orunsaturated hydrocarbon which may be unsubstituted or substituted with ahydroxyl, polyhydroxyl, aromatic, cycloaliphatic or mixed aromaticradical having about 1 to about 16 carbon atoms; R₁₄ is preferably astraight or branched chain, saturated or unsaturated hydrocarbon radicalhaving about 1 to about 5 carbon atoms; c is preferably 1-3; d ispreferably 1-4; and e is preferably 0-25.

The method is especially suitable for the manufacture of alkyl- andalkenyl bis(glyca)succinamide compounds wherein W is more preferably CH₂or an oxygen atom (O); X is more preferably hydrogen (H), or an alkylgroup having 1 carbon atom; Y is more preferably an oxygen (0) atom; Zis more preferably a CH═CH or CH₂ CH₂ group; R₉ is more preferably astraight chain saturated hydrocarbon which may be unsubstituted orsubstituted with an aromatic, cycloaliphatic or mixed aromatic radicalcomprising from about 3 to about 23 carbon atoms; R₁₃ is more preferablyhydrogen (H), a straight or branched chain saturated or unsaturatedhydrocarbon which may be unsubstituted or substituted with a hydroxyl,or polyhydroxyl group having about 1 to about 6 carbon atoms; R₁₄ ismore preferably a straight or branched chain, saturated or unsaturatedhydrocarbon radical having about 1 to about 5 carbon atoms; c is morepreferably 1-2; d is more preferably 1-4; and e is more preferably 0-15.

Examples of glycamines (1-amino-1-deoxyalditols,2-amino-2-deoxyketitols, 1-alkylamino-1-deoxyalditols etc.) suitable forthis method include those of the formula: ##STR85## wherein G ishydrogen (H), a (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) H group, a mono-,di-, oligo- or polysaccharide or mixtures thereof; a and b are each fromabout 0 to about 35 and the sum of a and b are from about 0 to about 35;n is from about 1 to about 6, m is from about 0 to about 8 and the sumof n and m are from about 0 to about 10; and R₁₃ is hydrogen (H), astraight or branched chain saturated or unsaturated hydrocarbon whichmay be unsubstituted or substituted with a hydroxyl, polyhydroxyl,aromatic, cycloaliphatic or mixed aromatic radical having about 1 toabout 31 carbon atoms. Illustrative of this class include, but are notlimited to glyceramine, erythramine, threamine, ribamine, arabinamine,xylamine, lyxamine, allamine, altramine, glucamine(1-amino-1-deoxyglucitol), mannamine, gulamine, idamine, galactamine,talamine, glucoheptamine (1-amino-1-deoxyglucoheptitol),1-amino-1-deoxyglyceroglucoheptitol,1-amino-1-deoxyglycergalactoheptitol,1-amino-1-deoxyglyceromannoheptitol, 1,3-dihydroxy-2-propylamine,erythrulamine (threulamine or glycerotetrulamine), ribulamine(erythropentulamine), xylulamine (threopentulamine), psicamine,fructamine (levulamine or 2-amino-2-deoxyfructitol), sorbamine(2-amino-2-deoxysorbitol), tagatamine, 2-amino-2deoxyalloheptulitol,3-amino-3-deoxyaltro-3-heptulitol, 2-amino-2-deoxymannoheptulitol,2-amino-2-deoxysedoheptulitol, 2-amino-2-deoxytaloheptulitol,2-amino-2-deoxyglycerogalactooctulitol,2-amino-2-deoxyglyceromannooctulitol,2-amino-2-deoxyerythrogalactononulitol,2-amino-2-deoxyerythroglucononulitol, lactamine[galactopyranosyl-β-(1-4)-1-amino1-deoxyglucitol], maltamine[glucopyranosyl-α-(1-4)-1-amino-1-deoxyglucitol], isomaltamine-A[glucopyranosyl-α-(1-6)-1-amino-1-deoxyglucitol], isomaltamine-B[glucopyranosyl-α-(1-6)-2-amino-2-deoxyfructitol], isomaltulamine[palatinamine or glucopyranosyl-α-(1-6)-2-amino-2-deoxyfructitol],cellobiamine [glucopyranosyl-β-(1-4)-1-amino-1-deoxyglucitol],leucramine [glucopyranosyl-α-(1-5)-2-amino-2-deoxyfructitol],gentiobiamine [glucopyranosyl-β-(1-6)-1-amino-1-deoxyglucitol],laminarbiamine [glucopyran-osyl-β-(1-3)-1-amino-1-deoxyglucitol],xylobiamine [xylopyranosyl-β-(1-4)1-amino-1-deoxyxylitol], inulobiamine[fructopyranosyl-β-(2-1 )-2-amino-2deoxyfructitol], mannobiamine[mannopyranosyl-β-(1-4)-1-amino-1-deoxymannitol], 3-ketopalatinamine[3-ketoglucopyranosyl-α-(1-6)-2-amino-2-deoxyfructitol],arabinofuranosyl-α-(1-3)- 1-amino-1-deoxyarabinitol,galactopyranosyl-α-(1-3)-1-amino-1-deoxygalactitol, maltotriamine[glucopyr-anosyl-α-(1-4)-glucopyranosyl-α-(1-4)-1-amino-1-deoxyglucitol],cellotriamine [glucopyranosyl-β-(1-4)-glucopyranosyl-β-(1-4)-1-amino-1-deoxyglucitol], panosamine[glucopyranosyl-α-(1-6)-glucopyranosyl-α-(1-4)-1-amino-1-deoxyglucitol], maltoheptamine[glucopyranosyl-α-(1-4)-{glucopyranosyl-α-(1-4)₅-1-amino-1-deoxyglucitol], starchamine, dextramine, cellulamine,2-amino-2-deoxyglucitol (2-amino-2-deoxysorbitol),3-amino-3-deoxyglucitol, 4-amino-4-deoxyglucitol,6-amino-6-deoxyglucitol, 3-amino-3-deoxyribitol,2-amino-2-deoxygalactitol, 2-amino-2-deoxymannitol,2-amino-2-deoxyallitol, 5-amino-5-deoxyaltritol,6-amino-6-deoxyerythrogalactooctitol, methylglucamine(1-methylamine-1-deoxyglucitol or 1-methylamine-1-deoxysorbitol),ethylglucamine, propylglucamine, butylglucamine, hydroxyethylglucamine,coconutglucamine, disorbitylamine, methyllactamine[galactopyranosyl-β-(1-4)-1-methylamino-1-deoxyglucitol],methylmaltamine [glucopyranosyl-α-(1-4)-1-methylamino-1-deoxyglucitol],ethyllactamine, propyllactamine, butyllactamine, hydroxyethyllactamine,coconutlactamine, ethylmaltamine, propylmaltamine, butylmaltamine,coconutmaltamine, pentylmaltamine, methyloxypropylglucamine,methyloxypropyllactamine, methyloxypropylmaltamine and C₂ -C₁₈oxypropylglucamine.

Examples of other glycamines (1-amino-1,6-dideoxyalditols and1-alkylamino-1,6-dideoxyalditols) suitable for this method include thoseof the formula: ##STR86## wherein G is hydrogen (H), a (CH₂ CH₂ O)_(a) Hor (CH₂ CHCH₃ O)_(b) H group, a mono-, di-, oligo- or polysaccharide ormixtures thereof; a and b are each from about 0 to about 35 and the sumof a and b are from about 0 to about 35; n is from about 1 to about 6, mis from about 0 to about 8 and the sum of n and m are from about 0 toabout 10; and R13 is hydrogen (H), a straight or branched chainsaturated or unsaturated hydrocarbon which may be unsubstituted orsubstituted with a hydroxyl, polyhydroxyl, aromatic, cycloaliphatic ormixed aromatic radical having about 1 to about 31 carbon atoms.Illustrative of this class include, but are not limited to1-amino-1,6-dideoxyallitol, 1-amino-1,6-dideoxyaltritol,1-amino-1,6-dideoxyglucitol, 1-amino-1,6-dideoxygulitol,1-amino-1,6-di-deoxytalitol, 1-amino-1,6-dideoxyfucitol, 1-amino-1,6-dideoxyrhamnitol, 1-methylamino-1,6-dideoxyrhamnitol,1-ethylamino-1,6-dideoxyrhamnitol, 1-coconut-amino-1,6-dideoxyrhamnitol,1-methyloxypropylamino-1,6-dideoxyrhamnitol.

Still other examples of glycamines (1-amino-l-deoxyketoses and1-alkylamino-1-deoxyketoses) suitable for this method include those ofthe formula: ##STR87## wherein G is hydrogen (H), a (CH₂ CH₂ O)_(a) H or(CH₂ CHCH₃ O)_(b) H group, a mono-, di-, oligo- or polysaccharide ormixtures thereof; a and b are each from about 0 to about 35 and the sumof a and b are from about 0 to about o is from about 0 to about 2 and pis from about 0 to about 4; and R₁₃ is hydrogen (H), a straight orbranched chain saturated or unsaturated hydrocarbon which may beunsubstituted or substituted with a hydroxyl, polyhydroxyl, aromatic,cycloaliphatic or mixed aromatic radical having about 1 to about 31carbon atoms. These glycamines are described as Amadori rearrangementproducts and methods for preparing such are disclosed in Methods inCarbohydr. Chem. 2, 99, (1963) to Hodge and Fisher which is incorporatedherein by reference. Illustrative of this class include, but are notlimited to 1-amino-1-deoxyribulose, 1-amino-1-deoxyxylulose,1-amino-1-deoxypsicose, 1-amino-1-deoxyfructose(1-amino-1-deoxylevulose), 1-amino-1-deoxyfructose hydrochloride,1-amino-1-deoxyfructose acetate salt, 1-amino-l-deoxyfructose oxalatesalt, 1-amino-1-deoxysorbose, 1-amino-1-deoxytagatose,1-amino-1-deoxyalloheptulose, 1-amino-1-deoxymannoheptulose,1-amino-1-deoxysedoheptulose, 1-amino-1-deoxytaloheptulose,1-amino-1-deoxyglycerogalactooctulose,1-amino-1-deoxyglyceromannooctulose,1-amino-1-deoxyerythrogalactononulose,galactopyranosyl-β-(1-4)-1-amino-1-deoxyfructose,glucopyranosyl-α-(1-4)-1-amino-1-deoxyfructose,glucopyranosyl-β-(1-4)-glucopyranosyl-β-(1-4)-1-amino-1-deoxyfructose,glucopyranosyl-α-(1-4)-{glucopyranosyl-α-1-4)}₄-1-amino-1-deoxyfructose, 1-methylamino-1-deoxyfructose hydrochloride,1-ethylamino-1-deoxyfructose acetate salt, 1-propylamino-1-deoxyfructoseoxalate salt, 1-hydroxypropylamino-1-deoxyfructose1-coconutamino-1-deoxyfructose, 1-tallowamino-1-deoxyfructose, 1-C₁ -C₁₈-alkyloxypropylamino-1-deoxyfructose, 1-C₁ -C₁₈alkyloxypropylaminopropylamino-1-deoxyfructose,1-methylamino-1-deoxyfructose, 1-ethylamino-1-deoxyfructose,1-propylamino- 1-deoxyfructose, 1-hexylamino- 1-deoxyfructose and1-octylamino-1-deoxyfmctose.

Still other examples of glycamines (1-amino-1-deoxyaldoses,2-amino-2-deoxyketoses, 1-alkylamino-1-deoxyaldoses and2-alkylamino-2-deoxyketoses) suitable for this method include those ofthe formula: ##STR88## wherein G is hydrogen (H), a (CH₂ CH₂ O)_(a) H or(CH₂ CHCH₃ O)_(b) H group, a mono-, di-, oligo- or polysaccharide ormixtures thereof; a and b are each from about 0 to about 35 and the sumof a and b are from about 0 to about 35; o is from about 0 to about 2and p is from about 0 to about 4; and R₁₃ is hydrogen (H), a straight orbranched chain saturated or unsaturated hydrocarbon which may beunsubstituted or substituted with a hydroxyl, polyhydroxyl, aromatic,cycloaliphatic or mixed aromatic radical having about 1 to about 31carbon atoms. Illustrative of this class include, but are not limited to1-amino-1-deoxyribose, 1-amino-1-deoxyxylose, 1-amino-1-deoxyglucose,1-amino-1-deoxymannose, 1-amino-1-deoxygulose, 1-amino-1-deoxyidose,1-amino-1-deoxygalactose, 1-amino-1-deoxyglucoheptose,1-amino-1-deoxyglyceroglucoheptose, 2-amino-2-deoxyfrucose,2-amino-2deoxysorbose, 1-amino-1-deoxylactose[galactopyranosyl-β-(1-4)-1-amino-1-deoxyglucose],1-amino-1-deoxymaltose [glucopyranosyl-α-(1-4)-1-amino-1-deoxyglucose],1-amino-1-deoxymaltotriose[glucopyranosyl-α-(1-4)-glucopyranosyl-α-(1-4)-1-amino-1-deoxyglucose],1-amino-1-deoxymaltoheptose[glucopyranosyl-α-(1-4)-{glucopyranosyl-α-(1-4)}₅-1-amino-1-deoxyglucose], 1-methylamino-1-deoxyglucose,1-ethylamino-1-deoxyglucose, 1-propylamino-1-deoxyglucose, 1-butylamino-1-deoxyglucose, 1-coconutamino-1-deoxyglucose, 1-tallowamino-1-deoxyglucose, 1-methyloxypropylamino-1-deoxyglucose, 1-C₂ -C₁₈alkyloxypropylamino- 1-deoxyglucose, 1-methylamino-1-deoxylactose,1-ethylamino-1-deoxylactose, 1-propylamino-1-deoxylactose,1-butylamino-1-deoxylactose, 1-coconutamino-1-deoxylactose,1-methylamino-1-deoxymaltose, 1-ethylamino-1-deoxymaltose,1-propylamino-1-deoxymaltose, 1-hydroxyethylamino- 1-deoxymaltose,1-methyloxypropylamino-1-deoxymaltose, 1-coconutamino- 1-deoxymaltose,1-methylamino-1-deoxymaltotriose, 1-coconutamino-1-deoxymaltotriose and1-methylamino-1-deoxymaltopentiose.

Still other examples of glycamines (6-amino-6-deoxyaldoses,6-amino-6-deoxyketoses, 6-amino-6-deoxyglycosides,6-alkylamino-6-deoxyaldoses, 6-alkylamino-6-deoxyketoses,6-alkylamino-6-deoxyglycosides, etc.) suitable for this method includethose of the formula: ##STR89## wherein G is hydrogen (H), a (CH₂ CH₂O)_(a) H or (CH₂ CHCH₃ O)_(b) H group, a mono-, di-, oligo- orpolysaccharide or mixtures thereof; R₁₂ is hydrogen (H), or an alkyl,alkenyl or hydroxyalkyl group having about 1 to about 5 carbon atoms; aand b are each from about 0 to about 35 and the sum of a and b are fromabout 0 to about 35; o is from about 0 to about 2, p is from about 0 toabout 4 and q is from about 0 to about 3; and R13 is hydrogen (H), astraight or branched chain saturated or unsaturated hydrocarbon whichmay be unsubstituted or substituted with a hydroxyl, polyhydroxyl,aromatic, cycloaliphatic or mixed aromatic radical having about 1 toabout 31 carbon atoms. Illustrative of this class include, but are notlimited to 5-amino-5-deoxyribose, 5-amino-5-deoxyxylose,6-amino-6-deoxyallose, 6-amino-6-deoxyaltrose, 6-amino-6-deoxyglucose,6-amino-6-deoxyglucose hydrochloride, 6-amino-6-deoxymethylglucoside,6-amino-6-deoxyethylglucoside, 6-amino-6-deoxymannose,6-amino-6-deoxygulose, 6-amino-6-deoxyidose, 6-amino-6-deoxygalactose,6-amino-6-deoxytalose, 7-amino-7-deoxyglucoheptose,7-amino-7-deoxyglyceroglucoheptose, 7-amino-7-deoxyglycergalactoheptose,7-amino-7-deoxyglyceromannoheptose, 6-amino-6-deoxyfructose,7-amino-7-deoxyalloheptulose, 7-amino-7-deoxymannoheptulose,7-amino-7-deoxysedoheptulose, 7-amino-7-deoxytaloheptulose,8-amino-8-deoxyglycerogalactooctulose,8-amino-8-deoxyglyceromannooctulose,9-amino-9-deoxyerythrogalactononulose,9-amino-9-deoxyerythroglucononulose,galactopyranosyl-β-(1-4)-6-amino-6-deoxyglucose,6-amino-6-deoxygalactose-β-(1-4)-glucopyranose,6-amino-6-deoxygalactose-β-(1-4)-6-amino-6-deoxyglucose,glucopyranosyl-α-(1-4)-6-amino-6-deoxyglucose,6-amino-6-deoxyglucose-α-(1-4)-glucopyranose, 1-amino-1-deoxy-β-fructofuranosyl-α-glucopyranoside,6-amino-6-deoxy-β-fructofuranosyl-α-glucopyranoside,β-fructofuranosyl-α-6-amino-6-deoxyglucopyranoside andglucopyranosyl-α-(1-4)-{glucopyranosyl-α-(1-4)}₅-6-amino-6-deoxyglucose, 6-methylamino-6-deoxyglucose,6-ethylamino-6-deoxyglucose, 6-propyl-amino-6-deoxyglucose,6-butylamino-6-deoxyglucose, 6-coconutamino-6-deoxyglucose,6-hydroxyethylamino-6-deoxyglucose,6-methyloxypropyl-amino-6-deoxyglucose,6-methylamino-6-deoxymethylglucoside,6-ethyl-amino-6-deoxyethylglucoside,6-propylamino-6-deoxycoconutglucoside,6-butylamino-6-deoxymethylglucoside, 6-coconutamino-6-deoxyglucoside,6-hydroxyethylamino-6-deoxypropylglucoside and6-methyloxypropylamino-6-deoxymethylglucoside.

Many additional examples of glycamines that are useful in the presentinvention are described in "Carbohydrates" edited by Collins, publishedby Chapman and Hall Ltd., (1987) and "The Carbohydrates, Chemistry andBiochemistry" edited by Pigman and Horton, 2nd Edition, Volumes IA, IIA,IB and IIB, published by Academic Press Inc., (1972); all of which areincorporated herein by reference.

Of the above described glycamines, those of the following formulas aremost highly preferred: ##STR90## wherein G is hydrogen (H) or amonosaccharide; R12 is hydrogen (H) or an alkyl, alkenyl or hydroxyalkylgroup having from about i to about 4 carbon atoms; R13 is hydrogen (H),a straight or branched chain saturated or unsaturated hydrocarbon whichmay be unsubstituted or substituted with a hydroxyl, polyhydroxylradical having about I to about 6 carbon atoms; m=0; n=1-4; o=0-1; p=0-1and q=1.

Examples of suitable alkyl and alkenyl succinic anhydrides, alkyl andalkenyl succinic acids (dicarboxylic acids) and alkyl and alkenylsuccinic acid esters are those as described above.

It has been found, in accordance with the present invention, that novelalkyl- and alkenyl bis(glyca)succinamide surfactants may be readilyprepared by (Step IB) reacting alkyl- or alkenyl succinic anhydrideswith alcohols in the presence of an acid catalyst at elevatedtemperatures to give the corresponding alkyl- or alkenyl succinate whichis then (Step IIC) reacted with glycamines (sugar-NHR₁₃) in the presenceof a base catalyst at elevated temperatures.

DESCRIPTION OF THE ESSENTIAL PROCESS PARAMETERS OF STEP IB

Within the first step of the process of the invention, it is desirableto use water-free reaction components, although small amounts of water(from about 1% to about 2% by weight) can be tolerated. Also, within thefirst step of the process of the invention, the alcohol can be addedprogressively to the anhydride, or the anhydride can be addedprogressively to the alcohol, preferably however, both reagents areadded in full amount at the beginning of the reaction. The alcohol ispreferably used in molar excess relative to the anhydride. The molarratio of alcohol to alkyl- or alkylene anhydride is from about 150:1 toabout 2: 1, preferably from about 80:1 to about 3:1, more preferablyfrom about 40:1 to about 4:1.

The succinate is preferably in liquid to gel form, however crystalline,granular, solid, flake or paste form can be used as well.

The reaction can be performed at or below room temperature, howevershorter reaction times can be achieved at elevated temperature and isusually preferred. Favorable reaction temperatures are from about 20° C.to about 160° C., preferably from about 30° C. to about 140° C., mostpreferably from about 40° C. to about the boiling point of the alcohol(reflux) that is used for esterification of the anhydride. The reactioncan be carried out under reduced pressure to assist in the removal ofsolvent or alcohol, however, it is preferably carried out at atmosphericpressure and under an inert gas blanket such as nitrogen, argon orhelium, most preferably it is carried out at atmospheric pressure.

The catalyst used to accelerate the rate of the reaction is generallyclassified as an organic or inorganic acid. Examples of suitable acidcatalysts useful in the present method are those as described above.

The acid catalyst can be added at any time during the reaction, however,it is preferably added at the beginning of the reaction and in fullamount. The molar ratio of anhydride to acid catalyst is from about700:1 to about 1:1, preferably from about 350:1 to about 25:1, mostpreferably from about 250:1 to about 45:1.

The substrates are reacted with intensive stirring for several hours,preferably from about 24 hours to about 0.5 hour, more preferably fromabout 15 hours to about 1 hour, most preferably when the reaction isdeemed complete and is verified by an analytical technique such as thinlayer chromatography (TLC), infrared spectroscopy (IR), proton nuclearmagnet resonance (H1 NMR), carbon 13 nuclear magnet resonance (C13 NMR),direct chemical ionization mass spectrometry (DCI MS), gaschromatography mass spectrometry (GC MS) or high pressure liquidchromatography (HPLC). The catalyst is then neutralized with base whoseamount is sufficient to provide a pH in the range of about 6 to about11, preferably from about 7 to about 10, most preferably greater than 9.Neutralization may be done at temperatures from about 0° C. to about 35°C.

Excess alcohol is optionally removed by known procedures such as simpledistillation, vacuum distillation or rotaevaporation, or it may beallowed to remain with the finished product and used as a solvent forStep IIC.

DESCRIPTION OF THE ESSENTIAL PROCESS PARAMETERS OF STEP IIC

Within the second step of the process of the invention, it is desirableto use nearly water-free reaction components, however this is not anessential condition. Also, within the second step of the process of theinvention, the glycamine can be added progressively to the succinate, orthe succinate can be added progressively to the glycamine, or bothreagents can be added at the beginning of the reaction, preferablyhowever, the glycamine is added in full amount to the succinate. Theglycamine can be used in molar excess relative to the succinate, or thesuccinate can be used in molar excess relative to the glycamine,preferably however, as seen in Examples 23 through 27, the glycamine isused in molar excess relative to the succinate. The molar ratio ofglycamine to alkyl- or alkenyl succinate is from about 3:1 to about 1.5:1, preferably from about 2.5:1 to about 1.7:1, more preferably fromabout 2.1:1 to about 1.9:1.

The glycamine is preferably in crystalline to granular form, howeversolid, flake, paste, gel or liquid forms can be used as well.

The reaction may be performed at or below room temperature, howevershorter reaction times can be achieved at elevated temperature and isusually preferred. Favorable reaction temperatures are from about 20° C.to about 250° C., preferably from about 30° C. to about 220° C., mostpreferably from about 40° C. to about 200° C. The reaction can becarried out under reduced pressure to assist in the removal of solventor alcohol, however, it is preferably carried out at atmosphericpressure and under an inert gas blanket such as nitrogen, argon orhelium, most preferably it is carried out at atmospheric pressure.

The catalyst used to accelerate the rate of the reaction is generallyclassified as an organic or inorganic base. Examples of suitable basecatalysts useful in the present method are those as described above.

The base catalyst can be added at any time during the reaction, however,it is preferably added at the beginning of the reaction and in fullamount. The molar ratio of glycamine to base catalyst is from about500:1 to about 1:1, preferably from about 250:1 to about 5:1, mostpreferably from about 150:1 to about 10:1.

The substrates are reacted with intensive stirring for several hours,preferably from about 0.5 hour to about 20 hours, more preferably fromabout 1 hour to about 15 hours, most preferably when the reaction isdeemed complete and is verified by an analytical technique such as thinlayer chromatography (TLC), infrared spectroscopy (IR), proton nuclearmagnet resonance (H1 NMR), carbon 13 nuclear magnet resonance (C13 NMR),direct chemical ionization mass spectrometry (DCI MS), fast atombombardment mass spectrometry (FAB MS) or high pressure liquidchromatography (HPLC).

In general, an organic solvent can be used to perform the reaction (StepIB and Step IIC) of the present invention, however, these materials areusually not necessary and are therefore not preferred. However, when anorganic solvent is used, the quantity of solvent should be sufficient todissolve the carbohydrate and succinate, but otherwise this is not anessential condition. An organic solvent may become neccessary when heatsensitive carbohydrates are used (e.g., certain Z-deoxy-Z-aminoaldosesor ketoses). Typical levels of solvent used are from about 5% to about95%, preferably from about 15% to about 75%, most preferably from about30% to about 50% by weight of the total reaction mixture. Preferably thesolvent is removed (after the reaction is complete) by known proceduressuch as simple distillation, vacuum distillation or rotaevaporation.When water is added, it is generally used as a diluent making theproduct a pureable liquid. Typical levels of water used as a reactionsolvent or diluent are from about 5% to about 95%, preferably from about15% to about 65%, most preferably from about 25% to about 50% by weightof the total reaction mixture.

In general, the nonionic alkyl- and alkenyl bis(glyca)succinamidesurfactants of the present invention are usually isolated as solids orsemisolids, however, when syrups are obtained, crystallization may beenhanced by the addition of an organic solvent. The resulting product issubsequently filtered, washed with an organic solvent and air or vacuumdried.

Optionally, further purification of (solid) alkyl- and alkenylbis(glyca)succinamide surfactants can be performed by recrystallizationin an organic solvent. The amount of solvent used is sufficient todissolve the product, preferably with heating. The solution is thenslowly cooled until recrystallization is complete, subsequentlyfiltered, washed with an organic solvent and air or vacuum dried.

Examples of typical reaction solvents, crystallization solvents andrecrystallization solvents that useful in the present method are thoseas described above.

When the reaction is complete, the base catalyst may be optionallyneutralized with an organic or inorganic acid. Preferred neutralizingacids include hydrochloric acid, oxalic acid, tartaric acid, citricacid, formic acid, lactic acid, lauric acid, dodecenyl succinic acid,dodecylbenzenesulfonic acid and methanesulfonic acid. The amount ofneutralizing acid used will be that which is sufficient to provide a pHin the range of about 4 to about 9, preferably from about 5 to about 8,most preferably about 7. Neutralization may be done in water or in aninert organic solvent or mixtures thereof, at about 0° C. to about 35°C.

Bleaching is sometimes required in either Step IB or Step IIC of theprocess, but not always necessary, since compounds of the invention areusually of good color. Examples of suitable bleaching agents useful inthe present method are those as described above. Typical levels ofbleaching agent are from about 0.01% to about 10%, preferably from about0.02% to about 7%, even more preferably from about 0.03% to about 5% byweight of the total reaction mixture.

Color improvement may also be carried out in either Step IB or Step IICof the process by using reducing agents. Examples of suitable reducingagents useful in the present method are those as described above.Typical levels of reducing agent are from about 0.01% to about 12%,preferably from about 0.02% to about 9%, even more preferably from about0.03% to about 7% by weight of the total reaction mixture.

The glycasuccinimide compounds prepared by the method of the inventionare generally isolated as crystalline solids in good yield, good purityand desirable color.

EXAMPLES

In order to more fully illustrate the nature of the invention and themanner of practicing the same, the following examples are presented.These Examples are given solely for the purpose of illustration and arenot to be construed as being limiting to the present invention sincemany variations are possible without departing from the spirit and scopeof the invention. For example, the following pseudo-glycamines areconsidered to be equivalent to the glycamines of the invention and canbe easily used in the process of the invention to form new nonionicglycasuccinamide surfactants. Examples of pseudo-glycamines include, butare not limited to 1-amino-2-propanol, DL-2-amino-1-propanol,2-amino-2-methylpropanol, 3-amino- 1-propanol, 2-amino-1-butanol,4-amino- 1-butanol, 5-amino-1-pentanol, monoethanolamine,diethanolamine, 2-amino-2-methyl-1,3-propanol,2-amino-2-ethyl-1,3-propanediol [1,1-bis(hydroxymethyl)propylamine],3-amino-1,2-propanediol [1,2-dihydroxy-1-propylamine],3-methylamino-1,2-propanediol tris(hydroxyethyl)amine[2-amino-2-(hydroxymethyl)-1,3-propanediol],tris(hydroxymethyl)aminomethane and the like.

EXAMPLE 1 (COMPARATIVE)

Preparation of Dodecenyl Sorbitan Succinate Ester ##STR91##

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with D-sorbitol (15.0 g, 8.23×10⁻² mole, 99.9+% pure),distilled dodecenylsuccinic anhydride (21.9 g, 8.23×10-2 mole) andsodium methoxide (0.07 g, 1.30×10⁻³ mole). The reaction mixture washeated to 150° C. for 4 hours under a mild nitrogen blanket giving 33.6g (91.5% yield) of dodecenyl D-sorbitan succinate ester as a viscousdark amber syrup.

    ______________________________________                                        IR Analysis (cm-1, Nujol)                                                     cm-1      Functional Group                                                    ______________________________________                                        3700-3100 Hydrogen Bonded O--H Stretch                                        3000-2840 C--H and ═C--H Stretch                                          1745-1705 C═O Stretch (Ester and Acid)                                    1450 and 1375                                                                           CH.sub.3 Bend                                                       1465      CH.sub.2 Bend                                                       1300-975  C--O Stretch and ═C--H Out of Plane Bend                        720       CH.sub.2 Rock                                                       ______________________________________                                    

    ______________________________________                                        C13 NMR Analysis (δ, ppm, DMSO D6/TMS)                                  (δ)      Carbon Type                                                    ______________________________________                                        14.0           CH.sub.3                                                       22.4           CH.sub.2 CH.sub.3                                              28.8-29.3      (CH.sub.2).sub.6                                               31.2           CH.sub.2 CH.sub.2 CH.sub.3                                     31.6           >CH.sub.2 CH═CH                                            34.5-34.8      Succinate Ring (CHCH.sub.2)                                    59.5-88.3      Sugar Carbons                                                  126.2-125.8    CH═CH (Cis and Trans)                                      133.3-132.0    CH═CH (Cis and Trans)                                      176.6-171.0    COOCH2, COOCH, COOH                                            ______________________________________                                         δ Chemical Shift, DMSO D6/TMS = Dimethylsulfoxide/Tetramethylsilane

    ______________________________________                                        H1 NMR Analysis (δ, ppm, DMSO D6/TMS)                                   (δ)  Proton Type                                                        ______________________________________                                        0.9 t      CH.sub.3                                                           1.2 s      (CH.sub.2).sub.7, >CH.sub.2 CH═CH                              2.0-1.8 bd COOCH.sub.2, COOCH, CH═CHCH.sub.2 (CH.sub.2).sub.7             2.1-2.9 bm Succinate Ring (CHCH.sub.2)                                        3.3-4.4 bm Sugar Protons                                                      4.6-4.8 bm Sugar Protons                                                      4.9-5.1 m  Sugar Protons                                                      5.2-5.6 bm CH═CH (Cis and Trans)                                          ______________________________________                                         s = singlet, bd = broad doublet, t = triplet, m = multiplet and bm = broa     multiplet                                                                

    __________________________________________________________________________    DCI MS Analysis (NH3), Heating Rate = 150 mA/Min. 1.2 μg in                __________________________________________________________________________    Methanol                                                                      m/e Compound                           Ion                                    __________________________________________________________________________    146.0                                                                             D-Isosorbide + NH.sub.4.spsb.+     (L + 18) .sup.+                        164.0                                                                             D-Sorbitan + NH.sub.4.spsb.+       (M + 18) .sup.+                        284.1                                                                             Dodecenyl Succinic Anhydride + NH.sub.4.spsb.+                                                                   (N + 18) .sup.+                        302.0                                                                             Dodecenyl Succinic Acid + NH.sub.4.spsb.+                                                                        (P + 18) .sup.+                        430.1                                                                             Dodecenyl D-Isosorbide Succinate + NH.sub.4.spsb.+                                                               (Q + 18) .sup.+                        448.1                                                                             Dodecenyl D-Sorbitan Succinate + NH.sub.4.spsb.+                                                                 (R + 18) .sup.+                        558.4                                                                             Dodecenyl D-Diisosorbide Succinate + NH.sub.4.spsb.+                                                             (S + 18) .sup.+                        576.3                                                                             Dodecenyl D-Isosorbide Sorbitan Succinate + NH.sub.4.spsb.+                                                      (T + 18) .sup.+                        594.2                                                                             Dodecenyl D-Disorbitan Succinate + NH.sub.4.spsb.+                                                               (U + 18) .sup.+                        696.4                                                                             Didodecenyl D-Isosorbide Disuccinate + NH.sub.4.spsb.+                                                           (V + 18) .sup.+                        714.4                                                                             Didodecenyl D-Sorbitan Disuccinate + NH.sub.4.spsb.+                                                             (W + 18) .sup.+                        824.0                                                                             Didodecenyl D-Diisorbide Disuccinate + NH.sub.4.spsb.+                                                           (X + 18) .sup.+                        842.4                                                                             Didodecenyl Isosorbide Sorbitan Disuccinate + NH.sub.4.spsb.+                                                    (Y + 18) .sup.+                        860.0                                                                             Didodecenyl Disorbitan Disuccinate + NH.sub.4.spsb.+                                                             (Z + 18) .sup.+                        __________________________________________________________________________     ##STR92##                                                                     ##STR93##                                                                     ##STR94##                                                                     ##STR95##                                                                     ##STR96##                                                                     ##STR97##                                                                

Preparation of Dodecenyl D-Glucosuccinimide ##STR98##

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with recrystallized D-glucamine (14.6 g, 8.06×10⁻² mole,99.9+% pure), distilled dodecenyl succinic anhydride (21.5 g, 8.06×10⁻²mole) and sodium methoxide (0.07 g, 1.30×10⁻³ mole). The reactionmixture was heated to 150° C. for 4 hours under a mild nitrogen blanketgiving 34.1 g (98.5% yield) of dodeceyl D-glucosuccinimide as acrystalline solid.

    ______________________________________                                        IR Analysis (cm-1, Nujol)                                                     cm-1     Functional Group                                                     ______________________________________                                        3660-3070                                                                              Hydrogen Bonded O--H Stretch                                         3000-2820                                                                              C--H and ═C--H Stretch                                           1770 and 1700                                                                          C═O Asymmetric and Symmetric Stretch (Imide)                     1450 and 1375                                                                          CH.sub.3 Bend                                                        1465     CH.sub.2 Bend                                                        1200-1000                                                                              C--O Stretch                                                         980-890  ═C--H Out of Plane Bend                                          720      CH.sub.2 Rock                                                        ______________________________________                                    

    ______________________________________                                        C13 NMR Analysis (δ, ppm, DMSO D6/TMS)                                  Estimated C13 Spectrum (δ)                                                               Found (δ)                                                                            Carbon #                                        ______________________________________                                        14.1             14.0         17                                              22.7             22.2         16                                              27.3-29.5        28.6-29.1    14                                              30.5             31.5         11                                              32.0             32.0         15                                              35.5             33.2         8                                               39.8             Under DMSO   9                                               46.1             41.7         6                                               64.9             63.4         1                                               70.9             69.3         5                                               71.9             69.9         4                                               71.9             71.6         3                                               71.9             71.9         2                                               128.6            125.4 (Cis)  13                                              128.6            125.8 (Trans)                                                                              13                                              136.2            132.4 (Cis)  12                                              136.2            133.5 (Trans)                                                                              12                                              173.7            176.8        10                                              174.6            179.6        7                                               ______________________________________                                         ##STR99##                                                                

    ______________________________________                                        H1 NMR Analysis (δ, ppm, DMSO D6/TMS)                                   (δ)      Proton Type                                                    ______________________________________                                        0.9 t          C H.sub.3                                                      1.2 s          (C H.sub.2).sub.7, >C H.sub.2 CH═CH                        1.9-2.0 bm     C H.sub.2 N, CH═CHC H.sub.2 (CH.sub.2).sub.7               2.1-2.9 m      Succinate Ring (C HC H.sub.2)                                  3.2-3.7 m      Sugar Protons                                                  3.8-3.9 bm     Sugar Protons                                                  4.3-4.4 m      Sugar Protons                                                  4.5 d          Sugar Protons                                                  4.8 d          Sugar Protons                                                  5.2-5.6 m      C H═C H (Cis and Trans)                                    ______________________________________                                         s = singlet, d = doublet, t = triplet, m = multiplet and bm = broad           multiplet                                                                

    __________________________________________________________________________    FAB MS Analysis                                                               m/e Compound                 Ion                                              __________________________________________________________________________    358.2                                                                             Dodecenyl D-Glucosuccinimide -4 H.sub.2 O                                                              (M + 1 -72) .sup.+                               376.2                                                                             Dodecenyl D-Glucosuccinimide -3 H.sub.2 O                                                              (M + 1 -54) .sup.+                               394.2                                                                             Dodecenyl D-Glucosuccinimide -2 H.sub.2 O                                                              (M + 1 -36) .sup.+                               412.2                                                                             Dodecenyl D-Glucosuccinimide -1 H.sub.2 O                                                              (M + 1 -18) .sup.+                               430.2                                                                             Dodecenyl D-Glucosuccinimide +1                                                                        (M + 1) .sup.+                                   452.2                                                                             Dodecenyl D-Glucosuccinimide +Na .sup.+                                                                (M + 23) .sup.+                                  593.3                                                                             Dodecenyl D-Bis(gluco)succinamide -1 H.sub.2 O                                                         (N + 1 -18) .sup.+                               611.3                                                                             Dodecenyl D-Bis(gluco)succinamide +1                                                                   (N + 1) .sup.+                                   633.3                                                                             Dodecenyl D-Bis(gluco)succinimide +Na .sup.+                                                           (N + 23) .sup.+                                  718.3                                                                             Didodecenyl D-Glucosuccinimidesuccinate +Na .sup.+                                                     (P + 23) .sup.+                                  __________________________________________________________________________     ##STR100##                                                                    ##STR101##                                                                    ##STR102##                                                                    Wherein X = H, or C.sub.16 H.sub.27 O.sub.3 (Succinate)                  

    ______________________________________                                        HPLC Analysis                                                                 Compound                 Purity                                               ______________________________________                                        D-Glucamine              0.22%                                                Didodecenyl D-Glucosuccinimidesuccinate                                                                1.38%                                                Dodecenyl D-Bis(gluco)succinamide                                                                      2.09%                                                Dodecenyl D-Glucosuccinimide                                                                           96.31%                                               ______________________________________                                         Column: Two 4.6 mm × 15 cm (Hexyl Regis Columns)                        Partical Size: 5 μm                                                        Mobil Phase: 30% Methanol/30% Acetonitrile/40% Water Containing 14.0 g/L      Sodium Perchlorate                                                            Detector: Refractive Index Detector                                           pH = 2.1 with Phosphoric Acid                                                 Sample Size: 0.0430 g/25 ml                                                   Flow Rate: 1.4 ml/min                                                         Temperature: 35° C.                                               

Discussion of Examples 1 and 2

As seen in comparative Example 1, pior art methods provide anionicsurfactants as a mixture of several different compounds resulting in theproduction of a thick viscous amber syrup which is difficult to handleand isolate. Whereas the method of the present invention, Example 2, canprovide solid nonionic surfactants in good yield, high purity anddesirable color without hydroxyl group protection, oligomerization orpolymerization. The method of the present invention is a significantimprovement over prior art methods.

EXAMPLE 3

Preparation of Commercial Grade Dodecenyl D-Glucosuccinimide

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with D-glucamine (20.0 g, 0.11 mole), dodecenyl succinicanhydride (29.4 g, 0.11 mole) and sodium methoxide (0.10 g, 1.85×10⁻³mole). The reaction mixture was heated to 150° C. for 6 hours under amild nitrogen blanket giving 46.0 g (97.0% yield) of dodecenylD-glucosuccinimide as a crystalline solid.

EXAMPLE 4

Preparation of Dodecenyl D-Glucosuccinimide in the Presence of aReaction Solvent and Recrystallizing Solvent

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and condensor is charged withD-glucamine (10.0 g, 5.52×10⁻² mole) dodecenyl succinic anhydride (14.7g, 5.52×10⁻² mole), sodium methoxide (0.05 g, 9.26×10⁻⁴ mole) andt-butanol (25 ml). The reaction mixture was heated to reflux (108° C.)for several hours and the solvent removed by vacuum distillation (50 mmHg) to a maximum temperature of 150° C. The reaction mixture was cooledto room temperature and recrystallized from ethyl acetate (100 ml). Theproduct was filtered, washed with cold ethyl acetate (3×20 ml) and driedunder vacuum giving 18.4 g (77.6% yield) of dodecenyl D-glucosuccinimideas a crystalline solid.

EXAMPLE 5

Preparation of Dodecenyl D-Glucosuccinimide in the Presence of a ColorImprovement Agent

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with D-glucamine (20.0 g, 0.11 mole), dodecenyl succinicanhydride (29.4 g, 0.11 mole), sodium borohydride (0.02 g, 5.29×10⁻⁴mole) and sodium methoxide (0.05 g, 9.26×10⁻⁴ mole). The reactionmixture was heated to 145° C. for 6 hours under a mild nitrogen blanketgiving 46.3 g (97.7% yield) of dodecenyl D-glucosuccinimide as acrystalline solid.

EXAMPLE 6

Preparation of Dodecyl D-Glucosuccinimide

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with D-glucamine (10.0 g, 5.52×10⁻² mole), dodecyl succinicanhydride (14.8 g, 5.52×10⁻² mole) and sodium methoxide (0.07 g,1.30×10⁻³ mole). The reaction mixture was heated to 170° C. for 6 hoursunder a mild nitrogen blanket giving 23.6 g (99.1% yield) of dodecylD-glucosuccinimide as a crystalline solid.

EXAMPLE 7

Preparation of Tetradecenyl D-Glucosuccinimide

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with D-glucamine (10.6 g, 5.58×10⁻² mole), tetradecenylsuccinic anhydride (17.2 g, 5.58×10⁻² mole) and sodium methoxide (0.06g, 1.11×10⁻³ mole). The reaction mixture was heated to 175° C. for 6hours under a mild nitrogen blanket giving 25.5 g (95.3% yield) ofteradecenyl D-glucosuccinimide as a crystalline solid.

EXAMPLE 8

Preparation of Tetradecyl D-Glucosuccinimide

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with D-glucamine (10.0 g, 5.52×10⁻² mole), tetradecylsuccinic anhydride (16.4 g, 5.52×10⁻² mole) and anhydrous potassiumcarbonate (0.2 g, 1.45×10⁻³ mole). The reaction mixture was heated to185° C. for 7 hours under a mild nitrogen blanket giving 23.7 g (93.4%yield) of tetradecyl D-glucosuccinimide as a crystalline solid.

EXAMPLE 9

Preparation of Decenyl D-Glucosuccinimide

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with D-glucamine (15.0 g, 8.82×10⁻² mole), decenyl succinicanhydride (19.7 g, 8.82×10⁻² mole) and sodium methoxide (0.08 g,1.48×10⁻³ mole). The reaction mixture was heated to 150° C. for 4 hoursunder a mild nitrogen blanket giving 32.8 g (98.7% yield) of decenylD-glucosuccinimide as a crystalline solid.

EXAMPLE 10

Preparation of Decyl D-Glucosuccinimide

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with D-glucamine (15.0 g, 8.82×10⁻² mole), decyl succinicanhydride (19.9 g, 8.82 x 10-2 mole) and sodium methoxide (0.08 g,1.48×10⁻³ mole). The reaction mixture was heated to 150° C. for 5 hoursunder a mild nitrogen blanket giving 32.6 g (97.6% yield) of decylD-glucosuccinimide as a crystalline solid.

EXAMPLE 11

Preparation of Octenyl D-Glucosuccinimide

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with D-glucamine (10.0 g, 5.52×10⁻² mole), octenyl succinicanhydride (11.6 g, 5.52×10⁻² mole) and sodium methoxide (0.05 g,9.26×10⁻⁴ mole). The reaction mixture was heated to 135° C. for 6 hoursunder a mild nitrogen blanket giving 20.3 g (98.5% yield) of octenylD-glucosuccinimide as a crystalline solid.

EXAMPLE 12

Preparation of Octyl D-Glucosuccinimide in the Presence of a ColorImprovement Agent

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with D-glucamine (10.0 g, 5.52×10⁻² mole), octyl succinicanhydride (11.7 g, 5.52×10⁻² mole), sodium methoxide (0.05 g, 9.26×10⁻⁴mole), sodium borohydrate (0.01 g, 2.64×10⁻⁴ mole) and sodiummetabisulfite (0.005 g, 2.63×10⁻⁵ mole). The reaction mixture was heatedto 140° C. for 6 hours under a mild nitrogen blanket giving 19.9 g(96.0% yield) of octyl D-glucosuccinimide as a crystalline solid.

EXAMPLE 13

Preparation of Decenyl 6-Imino-6-Deoxy-α-D-MethylglucopyranosideSuccinate

a.) 6-0-p-Tolylsulfonyl-α-D-Methylglucopyranoside

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with methyl α-D-glucopyranoside (6.0 g, 3.09×10⁻² mole) andanhydrous pyridine (55 ml) under a mild nitrogen blanket. The solutionwas cooled to 0° C. and p-toluenesulfonyl chloride (6.3 g, 3.30×10⁻²mole) dissolved in pyridine (15 ml) was added dropwise. The reactionmixture was allowed to stir at room temperature for about 2 days and thepyridine was removed by vacuum distillation. The resulting residue wasdissolved in chloroform (75 ml) and washed with an aqueous solution ofpotassium hydrogen sulfate and potassium hydrogen carbonate. Thechloroform was removed by rotaevporation and the resulting syrupdissolved in toluene (100 ml) at reflux, afterwhich, a precipate formedupon cooling which was filtered, washed with cold toluene (3×25 ml) anddried under vacuum giving 5.6 g (51.9% yield) of6-O-p-tolylsulfonyl-α-D-methylglucopyranoside with a melting point of117°-119° C.

b.) 6-Amino-6-Deoxy-α-D-Methylglucopyranoside

A 250 ml two necked round bottom flask equipped with a nitrogen outletand inlet was charged with a solution of6-O-p-tolylsulfonyl-α-D-methylglucopyranoside (5.0 g, 1.44×10⁻² mole)dissolved in methanol (180 ml) and cooled to 0° C. The solution wassaturated with anhydrous ammonia and charged to an 300 ml autoclavewhich was heated for 1 day at 120° C. The solution was treated withcharcoal, refluxed for 2 hours, filtered over celite and washed withmethanol (3×35 ml). The solution was then treated with AmberliteIRA-401S ion-exchange resin, stirred, filtered and the solvent(methanol) removed by rotaevaporation giving 2.5 g (89.9% yield) of6-amino-6-deoxy-α-D-methylglucopyranoside as a syrup.

c.) Decenyl 6-Imino-6-Deoxy-α-D-Methylglucopyranoside Succinate##STR103##

A 25 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with 6-amino-6-deoxy-α-D-methylglucopyranoside (2.0 g,1.04×10⁻² mole), decenyl succinic anhydride (2.5 g, 1.04×10⁻² mole) andsodium methoxide (0.007 g, 1.30×10⁻⁴ mole). The reaction mixture washeated to 135° C. for 6 hours under a mild nitrogen blanket giving 4.4 g(97.8% yield) of decenyl 6-imino-6-deoxy-α-D-methylglucopyranosidesuccinate.

EXAMPLE 14

Preparation of Dodecenyl 3-Imino-1,2-Propanediol Succinate ##STR104##

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with 3-amino-l,2-propandiol (8.0 g, 8.78×10⁻² mole),dodecenyl succinic anhydride (23.4 g, 8.78×10⁻² mole) and sodiummethoxide (0.05 g, 9.26×10⁻⁴ mole). The reaction mixture was heated to135° C. for 6 hours under a mild nitrogen blanket giving 28.3 g (94.9%yield) of dodecenyl 3-imino-1,2-propanediol succinate.

EXAMPLE 15

Preparation of Dodecenyl Monoethanolsuccinimide/DodecenylD-Glucosuccinamide

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer, nitrogen inlet and short path distillation headwas charged with monoethanolamine (5.0 g, 8.19×10⁻² mole), D-glucamine(3.7 g, 2.05×10⁻² mole), dodecenyl succinic anhydride (27.3 g, 0.10mole) and sodium methoxide (0.05 g, 9.26×10⁻⁴ mole). The reactionmixture was heated to 135° C. for 6 hours under a mild nitrogen blanket.

EXAMPLES 16-17

The Physical Chemistry of Alkyl- and Alkenyl D-Glycasuccinimides

There are several unique characteristic properties that distinguishsurface-active materials (surfactants) from other non-surface activematerials. These include critical micelle concentration and surfacetension reduction. The following examples will show that the alkyl- andalkenyl D-glyca-succinimides of the invention to be surface-active andare therefore considered to be a new class of sugar based surfactant.

EXAMPLE 16

Critical Micelle Concentration

The critical micelie concentration (CMC) is defined as the concentrationat which a surfactant forms micelles in aqueous solution. Micellizationis the preferred interfacial phenomena, since certain surfactantbenefits such as foam production depend on the formation of theseaggregates in solution. Materials that do not form micelles do notprovide any foam.

The CMC value of dodecenyl D-glucosuccinimide was determined by plottingsurface tension as a function of log(concentration) and extrapolatinglinear points to obtain an intersection point. The concentration at thispoint was taken as the CMC. The technique used was the Wilhelmy platemethod and the instrument used was a Lauda Auto-Tensiometer. Whilewishing not to be bound to theory, it is believed that surfactants withlow CMC values form micelles more readily at lower concentrations thanthose with high CMC values.

The critical micelie concentration (CMC) value of dodecenylD-glucosuccinimide (molecular weight=447.56 g/mole) was determined andis set forth below:

    __________________________________________________________________________    The Critical Micelle Concentration of Dodecenyl D-Glucosuccinimide            Entry                                                                             Surfactant      CMC       Temperature (°C.)                        __________________________________________________________________________    1   Dodecenyl D-Glucosuccinimide                                                                  0.12 mM (0.0054%)                                                                       25                                              2   Triton X-100.sup.a                                                                            0.24 mM (0.0145%)                                                                       25                                              3   Nonidet P-40.sup.b                                                                            0.29 mM (0.0175%)                                                                       25                                              __________________________________________________________________________     .sup.a Triton X100 is a commercial nonionic surfactant [polyoxyethylene       (9.5) ptert-octyl-phenyl ether] sold by Union Carbide Chemical Company.       .sup.b NonidetP-40 is a commercial nonionic surfactant [polyoxyethylene       (9.0) ptert-octyl-phenyl ether] available through Sigma Chemical Company.

A necessary and sufficient condition for CMC formation and surfacetension reduction is the presence of both hydrophilic and hydrophobicfunctional groups. The hydrophilic portion provides strong interactionbetween the surfactant at the interface and with the surrounding waterphase. The hydrophobic portion provides spontaneous adsorption of thesurfactant at the interface and strong interaction with the adjacent airphase. If any of these functions are not performed, then CMC formationand surface tension reduction will not occur. For significant surfaceactivity, a properly balanced hydrophilic and hydrophobic character isessential. From the above table, it can be seen that dodecenylD-glucosuccinimide is properly balanced and forms micelles at asurprising low critical micelie concentration which is comparable toTriton X-100 and Nonidet P-40, two common petrochemically derivednonionic surfactants. This finding suggests that the alkyl- and alkenylD-glycasuccinimide compounds of the invention are surface-active.

EXAMPLE 17

Surface Tension Reduction

An important characteristic feature that surfactants have is thetendency for them to absorb at the water/air interface in an orientedmanner, thereby altering the interfacial free energy of that surface.The surface free energy per unit area or surface tension (γ), is ameasure of this work and may be considered as the minimum amount of workrequired to bring sufficient surfactant molecules to the surface.

The surface tension (γ) value of dodecenyl D-glucosuccinimide wasdetermined and is set forth below:

    __________________________________________________________________________    Surface Tension of Dodecenyl D-Glucosuccinimide at the Water/Air              Interface                                                                     Entry                                                                             Surfactant      γ                                                                              Temperature (°C.)                           __________________________________________________________________________    1   Dodecenyl D-Glucosuccinimide                                                                  29.4 dyn/cm                                                                          25                                                 2   Water           72.0 dyn/cm                                                                          25                                                 __________________________________________________________________________

From the above table it can be seen that dodecenyl D-glucosuccinimideabsorbs strongly at the water/air interface resulting in a significantreduction in water surface tension. This finding suggests that thealkyl- and alkenyl D-glycasuccinimide compounds of the invention aresurface-active.

EXAMPLE 18

The Krafft Point of Alkyl- and Alkenyl D-Glycasuccinimides

The temperature at and above which surfactants begin to form micellesinstead of precipitates is referred to as the Kraft point (T_(k)) and atthis temperature the solubility of a surfactant becomes equal to its CMC(numerical value at which micelles are formed).

The appearance and development of micelles are important since certainsurfactant properties such as foam production depend on the formation ofthese aggregates in solution.

The Krafft point was measured by preparing 650 ml of a 0.1% dispersionof glycasuccinimide in water by weight. If the surfactant was soluble atroom temperature, the solution was slowly cooled to 0° C. If thesurfactant did not precipitate out of solution, its Krafft point wasconsidered to be <0° C. (less than zero). If the surfactant precipitatedout of solution, the temperature at which precipitation occurs was takenas the Krafft point.

If the surfactant was insoluble at room temperature, the dispersion wasslowly heated until the solution became homogeneous. It was then slowlycooled until precipitation occurred. The temperature at which thesurfactant precipitates out of solution upon cooling was taken as theKrafft point. The Krafft point of various alkyl- and alkenylD-glycasuccinimide compounds are as follows:

    ______________________________________                                        The Krafft Point (T.sub.k) of Alkyl- and Alkenyl D-Glucosuccinimides          Compound            T.sub.k (°C.), 0.1%                                ______________________________________                                        Octyl D-Glucosuccinimide                                                                          <0° C.                                             Octenyl D-Glucosuccinimide                                                                        <0° C.                                             Decyl D-Glucosuccinimide                                                                          <0° C.                                             Decenyl D-Glucosuccinimide                                                                        <0° C.                                             Dodecyl D-Glucosuccinimide                                                                        28° C.                                             Dodecenyl D-Glucosuccinimide                                                                      <5° C.                                             Tetradecyl D-Glucosuccinimide                                                                     33° C.                                             ______________________________________                                    

From the above table it can be seen that the alkyl- and alkenylglycasuccinimides of the invention are readily soluble in water and formmicelles at low temperatures.

EXAMPLE 19

The Foam Height of Alkyl- and Alkenyl D-Glycasuccinimides

Since most of the foaming data on surfactants is typically obtained bythe Ross-Miles method (Ross, J. and Miles, G. D. Am Soc. for TestingMaterial Method D1173-63 Philadelphia, Pa. (1953); Oil & Soap (1958)62:1260) the foaming ability of these surfactants were acquired usingthis method.

In the Ross-Miles method, 200 mL of a surfactant solution contained in apipette of specified dimensions with a 2.9-mm-i.d. orifice is allowed tofall 90 cm onto 50 mL of the same solution contained in a cylindricalvessel maintained at a given temperature by means of a water jacket. Theheight of the foam produced in the cylindrical vessel is readimmediately after all the solution has run out of the pipette and thenagain after a given amount of time.

Using this method, the foam production (initial foam height in mm) andfoam stability (final foam height after 10 minutes in mm) were measuredat 0.1% glycasuccinimide concentration, 40° C. and 0 ppm (parts permillion) hardness. The foam height of the of several alkyl- and alkenylD-glycasuccinimides are as follows:

    ______________________________________                                        The Foam Height (FH) of D-Glucosuccinimides (0 ppm Hardness)                                               Final                                            Compound          Initial FH FH (10 Min.)                                     ______________________________________                                        Octyl D-Glucosuccinimide                                                                        97         85                                               Octenyl D-Glucosuccinimide                                                                      99         86                                               Decyl D-Glucosuccinimide                                                                        210        193                                              Decenyl D-Glucosuccinimide                                                                      201        185                                              Dodecyl D-Glucosuccinimide                                                                      185        173                                              Dodecenyl D-Glucosuccinimide                                                                    172        153                                              Tetradecyl D-Glucosuccinimide                                                                   negligible negligible                                       ______________________________________                                    

From the above table it can be seen that the alkyl- and alkenylglycasuccinimides of the present invention provide a copious stable foamand are therefore surface-active.

EXAMPLE 20

Preparation of Dodecenyl Dimethylsuccinate ##STR105##

A 250 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer and condenser was charged with dodecenylsuccinicanhydride (15.0 g, 5.63×10⁻² mole), methanol (135.0 g, 4.21 moles for10% total solids) and methanesulfonic acid (4 drops). The reactionmixture was heated at reflux for 16 hours, cooled to room temperature,neutralized with 0.1N sodium methoxide in methanol followed by vacuumdistillation giving 16.4 g (99.0% yield, 94.3% purity by GC).

EXAMPLE 21

Preparation of Dodecyl Dimethylsuccinate

A 250 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer and condenser was charged with dodecylsuccinicanhydride (15.0 g, 5.59×10⁻² mole), methanol (150.0 g, 4.21 moles for9.1% total solids) and methanesulfonic acid (4 drops). The reactionmixture was heated at reflux for 24 hours, cooled to room temperature,neutralized with 0.1N sodium methoxide in methanol followed by vacuumdistillation giving 16.4 g (99.0% yield, 98.4% purity by GC)

EXAMPLE 22

Preparation of Tetradecenyl Dimethylsuccinate

A 250 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer and condenser was charged with tetradecenylsuccinicanhydride (8.6 g, 2.90×10⁻² mole), methanol (130.0 g, 4.21 moles for6.2% total solids) and methanesulfonic acid (3 drops). The reactionmixture was heated at reflux for 16 hours, cool to room temperature andneutralized with 0.1N sodium methoxide in methanol followed by vacuumdistillation giving 9.2 g (98.4% yield, 98.3% purity by GC)

EXAMPLE 23

Preparation of Dodecenyl Bis(Methyl D-Gluco)succinamide ##STR106##

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer and nitrogen inlet/outlet was charged with methylD-glucamine (6.6 g, 3.40×10⁻² mole), dodecenyl dimethylsuccinate (5.0 g,1.70×10⁻² mole, Example 20) and sodium methoxide (0.1 g, 1.85×10⁻²mole). The reaction mixture was heated to 140° C. for 6 hours under amild nitrogen blanket giving 9.9 g (93.8% yield).

EXAMPLE 24

Preparation of Dodecyl Bis(D-Gluco)succinamide ##STR107##

A 50 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer and nitrogen inlet/outlet was charged withD-glucamine (7.5 g, 4.12×10⁻² mole), dodecyl dimethylsuccinate (6.1 g,2.06×10⁻² mole, Example 21) and sodium methoxide (0.1 g, 1.85×10⁻²mole). The reaction mixture was heated to 140° C. for 6 hours under amild nitrogen blanket giving 11.6 g (94.7% yield).

EXAMPLE 25

Preparation of Dodecenyl Bis(Glycero)succinamide [DodecenylBis(3-Amido-1,2-Propandiol) Succinamide] ##STR108##

A 50 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer and nitrogen inlet/outlet was charged with3-amino-1,2-propanediol (3.1 g, 3.40×10⁻² mole), dodecenyldimethylsuccinate (5.0 g, 1.70×10⁻² mole, Example 20) and sodiummethoxide (0.1 g, 1.85×10⁻² mole). The reaction mixture was heated to130° C. for 6 hours under a mild nitrogen blanket giving 6.9 g (98.4%yield).

EXAMPLE 26

Preparation of Tetradecyl Bis(Methyl D-Gluco)succinamide/TetradecylBis(Monoethanol)succinamide

A 50 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer and nitrogen inlet/outlet was charged with methylD-glucamine (1.8 g, 9.25×10-3 mole), monoethanolamine (1.7 g, 2.77×10⁻²mole), tetradecenyl dimethylsuccinate (6.0 g, 1.85×10⁻² mole) and sodiummethoxide (0.1 g, 1.85×10⁻² mole). The reaction mixture was heated to135° C. for 8 hours under a mild nitrogen blanket giving 6.4 g (97.5%yield).

EXAMPLE 27

Preparation of Dodecenyl Bis(Methyl D-Gluco)succinamide ##STR109##

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer and nitrogen inlet/outlet was charged withdodecenylsuccinic anhydride (9.0 g, 3.38×10⁻² mole), methanol (50 ml,1.23 mole) and methanesulfonic acid (4 drops). The reaction mixture washeated under reflux for 6 hours followed by neutralization with sodiummethoxide dissolved in methanol (0.1N). To the mixture was added methylD-glucamine (13.2 g, 6.76×10⁻² mole) and sodium methoxide catalyst (0.1g, 1.85×10⁻³ mole). The reaction mixture was heated under reflux for 6hours and methanol removed by simple distillation. The reaction wasstirred for at 135° C. for 4 hours giving 19.5 g (92.9% yield)

EXAMPLE 28

Preparation of Dodecenyl Methyl D-Glucosuccinamide Methyl Succinate##STR110##

A 100 ml four necked round bottom flask equipped with a mechanicalstirrer, thermometer and nitrogen inlet/outlet was charged withdodecenylsuccinic anhydride (9.0 g, 3.38×10⁻² mole), methanol (50 ml,1.23 mole) and sulfuric acid (0.1 g). The reaction mixture was heated to60° C. for 4 hours followed by neutralization with sodium methoxidedissolved in methanol (1N). The solvent was removed by vacuumdistillation. To the reaction mixture was added methyl D-glucamine (6.6g, 3.38×10⁻² mole) and sodium methoxide catalyst (0.1 g, 1.85×10⁻³mole). The product was heated at 140° C. for 6 hours followed byneutralization with formic acid. The product was washed with acetonegiving 14.5 g (93.3% yield).

HOME APPLICATION AND USE

The nonionic glycasuccinamide and bis(glyca)succinamide surfactants ofthe present invention are useful in detergent, personal product, oralhygiene, food and pharmacological compositions which are available in avariety of types and forms. Preferred applications are detergent,personal product and oral hygiene compositions.

A classification according to detergent type would consist of heavy-dutydetergent powders, heavy-duty detergent liquids, light-duty liquids(dishwashing liquids), institutional detergents, specialty detergentpowders, specialty detergent liquids, laundry aids, pretreatment aids,after treatment aids, presoaking products, hard surface cleaners, carpetcleansers, carwash products and the like.

A classification according to personal product type would consist ofhair care products, bath products, cleansing products, skin careproducts, shaving products and deodorant/antiperspirant products.

Examples of hair care products include, but are not limited to rinses,conditioners shampoos, conditioning shampoos, antidandruff shampoos,antilice shampoos, coloring shampoos, curl maintenance shampoos, babyshampoos, herbal shampoos, hair loss prevention shampoos, hairgrowth/promoting/stimulating shampoos, hairwave neutralizing shampoos,hair setting products, hair sprays, hair styling products, permanentwave products, hair straightening/relaxing products, mousses, hairlotions, hair tonics, hair promade products, brilliantines and the like.

Examples bath products include, but are not limited to bath oils, foamor bubble bathes, therapeutic bathes, after bath products, after bathsplash products and the like.

Examples cleansing products include, but are not limited to showercleansers, shower gels, body shampoos, hand/body/facial cleansers,abrasive scrub cleansing products, astringent cleansers, makeupcleansers, liquid soaps, toilet soap bars, syndet bars and the like.

Examples skin care products include, but are not limited tohand/body/facial moisturizers, hand/body/facial creams, massage creams,hand/body/facial lotions, sunscreen products, tanning products,self-tanning products, aftersun products, masking products, lipsticks,lip gloss products, rejuvenating products, antiaging products,antiwrinkle products, anti-cellulite products, antiacne products and thelike.

Examples shaving products include, but are not limited to shavingcreams, aftershave products, preshave products and the like.

Examples deodorant/antiperspirant products include, but are not limitedto deodorant products, antiperspirant products and the like.

A classification according to oral hygiene type would consist of, but isnot limited to mouthwashes, pre-brushing dental rinses, post-bushingrinses, dental sprays, dental creams, toothpastes, toothpaste gels,toothpowders, dental cleansers, dental flosses, chewing gums, lozengesand the like.

A classification according to detergent, personal product and oralhygiene form would consist of aerosols, liquids, gels, creams, lotions,sprays, pastes, roll-on, stick, tablet, powdered and bar form.

A comprehensive list of essential and optional ingredients that areuseful in detergent, personal product and oral hygiene compositions aredescribed in McCutcheon's, Detergents and Emulsifiers (Vol 1) andMcCutcheon's, Functional Materials (Vol 2), 1992 Annual Edition,published by McCutcheon's MC Publishing Co. as well as the CTFA(Cosmetic, Toiletry and Fragrance Association) 1992 International BuyersGuide, published by CTFA Publications and OPD 1993 Chemical BuyersDirectory 80th Annual Edition, published by Schnell Publishing Co. whichare all incorporated herein by reference.

INDUSTRIAL APPLICATION AND USE

The glycasuccinamide and bis(glyca)succinamide compounds of theinvention are useful as surface-active agents (surfactants).

This invention has been described with respect to certain preferredembodiments and various modifications and variations in the lightthereof will be suggested to persons skilled in the art and are to beincluded within the spirit and purview of this application and the scopeof the appended claims. For example, it is known that under certainconditions, D-glucamine and methyl D-glucamine can loose water andcyclize to form sorbitan amine and sorbitan methylamine respectively,which can also react with alkyl and alkenyl succinic anhydrides or thierderivatives, to produce sorbitan succinamide surfactants. It is alsoknown, that under certain conditions, methyl D-glucamine can undergoesterfication with alkyl and alkenyl succinic anhydrides or thierderivatives, at the hydroxyl group instead of amidation at the methylamino group to produce ester linked succinate surfactants. Theseproducts may be present in low amounts in some cases and generally donot have any serious detrimental effects on the reaction.

What is claimed is:
 1. A nonionic alkyl- or alkenyl glycasuccinimidesurfactant compound having the formula: ##STR111## wherein A is selectedfrom the group consisting of the following structures which are attachedto the succinate ring via the nitrogen (N) atom on said structures;##STR112## wherein G is selected from the group consisting of hydrogen(H), a SO₃ M, PO₃ M₂, (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) H group, amono-, di-, oligo- or polysaccharide or mixtures thereof;wherein M isselected from the group consisting of hydrogen (H), an alkali metal,alkaline earth metal, ammonium, alkyl substituted ammonium or mono-,di-, trialkanolammonium group having about 1 to about 5 carbon atoms;wherein W is a CH₂ group, oxygen atom (O) or mixtures thereof; wherein Xis hydrogen (H), an alkyl group having about 1 to about 4 carbon atomsor mixtures thereof; wherein Y is a NR₁₀, +N(R₁₀)₂, O, S, SO, SO₂, COO,OOC, CONR₁₀, NR₁₀ CO group or mixtures thereof; wherein Z is a CH═CH,CH₂ CH₂ group or mixtures thereof; wherein R₉ is a straight or branchedchain saturated or unsaturated hydrocarbon which may be unsubstituted orsubstituted with an aromatic, cycloaliphatic or mixed aromatic radicalhaving about 1 to about 31 carbon atoms; wherein R₁₀ is hydrogen (H), ahydroxyl alkyl group having about 1 to about 6 carbon atoms, a straightor branched chain, saturated or unsaturated hydrocarbon which may beunsubstituted or substituted with an aromatic, cycloaliphatic or mixedaromatic aliphatic radical having about 1 to about 8 carbon atoms;wherein R₁₁ is hydrogen (H), or an alkyl, alkenyl or hydroxyalkyl grouphaving about 1 to about 6 carbon atoms; wherein R₁₂ is hydrogen (H), oran alkyl, alkenyl or hydroxyalkyl group having about 1 to about 6 carbonatoms; wherein a=0-35; b=0-35; c=1-3; d=1-5; e=0-35; m=0-8; n=1-6;o=0-2; p=0-4; q=0-3; r=0-3; and s=0-1.
 2. A compound according to claim1wherein A is selected from the group consisting of the followingstructures which are attached to the succinate ring via the nitrogen (N)atom on said structures: ##STR113## wherein G is selected from the groupconsisting of hydrogen (H), a (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) Hgroup, a mono-, di- or oligosaccharide or mixtures thereof; wherein W isa CH₂ group, oxygen atom (O) or mixtures thereof; wherein X is hydrogen(H), an alkyl group having about 1 to about 3 carbon atoms or mixturesthereof; wherein Y is a NR₁₀, +N(R₁₀)₂, O, COO, OOC group or mixturesthereof; wherein Z is a CH═CH, CH₂ CH₂ group or mixtures thereof;wherein R₉ is a straight or branched chain saturated or unsaturatedhydrocarbon which may be unsubstituted or substituted with an aromatic,cycloaliphatic or mixed aromatic radical having about 2 to about 25carbon atoms; wherein R₁₀ is hydrogen (H), a hydroxyl alkyl group havingabout 1 to about 4 carbon atoms, a straight or branched chain, saturatedor unsaturated hydrocarbon radical having about 1 to about 5 carbonatoms; wherein R₁₁ is hydrogen (H), or an alkyl, alkenyl or hydroxyalkylgroup having about 1 to about 5 carbon atoms; wherein R₁₂ is hydrogen(H), or an alkyl, alkenyl or hydroxyalkyl group having about 1 to about5 carbon atoms; wherein a=0-25; b=0-25 c=1-3; d=1-4; e=0-25; m=0-7;n=1-5; o=0-2; p=0-3; q=0-2; r=0-2; and s=0-1.
 3. A compound according toclaim 1wherein A is selected from the group consisting of the followingstructures which are attached to the succinate ring via the nitrogen (N)atom on said structures: ##STR114## wherein G is selected from the groupconsisting of hydrogen (H), a (CH₂ CH₂ O)_(a) H or (CH₂ CHCH₃ O)_(b) Hgroup, a mono- di- or oligosaccharide or mixtures thereof; wherein W isa CH₂ group, oxygen atom (O) or mixtures thereof; wherein X is hydrogen(H), an alkyl group having about 1 to about 2 carbon atoms or mixturesthereof; wherein Y is an oxygen atom (O) or a COO or OOC group ormixtures thereof; wherein Z is a CH═CH, CH₂ CH₂ group or mixturesthereof; wherein R₉ is a straight or branched chain saturatedhydrocarbon radical having about 3 to about 23 carbon atoms; wherein R₁₂is hydrogen (H), or an alkyl, alkenyl or hydroxyalkyl group having about1 to about 4 carbon atoms; wherein a=0-15; b=0-15; c=1-2; d=1-4; e=0-15;m=0-5; n=1-5; o=0-1; p=0-2; and q=0-2.
 4. A compound according to claim1wherein A is selected from the group consisting of the followingstructures which are attached to the succinate ring via the nitrogen (N)atom on said structures: ##STR115## wherein G is hydrogen (H); wherein Wis a CH₂ group, oxygen atom (O) or mixtures thereof; wherein X ishydrogen (H) or an alkyl group having 1 carbon atom; wherein Y is anoxygen atom (O); wherein Z is a CH═CH, CH₂ CH₂ group or mixturesthereof; wherein R₉ is a straight or branched chain saturatedhydrocarbon radical having about 4 to about 22 carbon atoms; wherein R₁₂is hydrogen (H), or an alkyl, alkenyl or hydroxyalkyl group having about1 to about 4 carbon atoms; wherein c=1; d=1-4; e=0-5; m=0; n=1-4; o=0-1;p=0-1; and q=1.
 5. A compound according to claim 1wherein A is selectedfrom the group consisting of the following structures which are attachedto the succinate ring via the nitrogen (N) atom on said structures:##STR116## wherein W is a CH₂ group, oxygen atom (O) or mixturesthereof; wherein X is hydrogen (H) or an alkyl group having 1 carbonatom; wherein Y is an oxygen atom (O); wherein Z is a CH═CH, CH₂ CH₂group or mixtures thereof; wherein R₉ is a straight or branched chainsaturated hydrocarbon radical having about 4 to about 22 carbon atoms;wherein c=1; d=1-4 and e=0-5.
 6. A compound according to claim 4 havingthe structure: ##STR117## wherein; A= ##STR118## G=hydrogen (H); R₉ =C₁₀H₂₁ ; W=oxygen (O); Z=CH₂ CH₂ ; c=1; e=0; m=0; and n=4.
 7. A compoundaccording to claim 4 having the structure: ##STR119## wherein; A=##STR120## G=hydrogen (H); R₉ =C₁₂ H₂₅ ; W=oxygen (O); X=hydrogen (H);Y=oxygen (O); Z=CH₂ CH₂ ; c=1; d=2; e=3; m=0; and n=4.
 8. A compoundaccording to claim 3 having the structure: ##STR121## wherein; A=##STR122## G=hydrogen (H) or (CH₂ CH₂ O)_(a) H group; R₉ =C₉ H₁₉ ; W=CH₂; Z=CH₂ CH₂ ; a=can vary from about 1 to about 8 for a total average of4; c=1; e=0; m=0; and n=4.
 9. A compound according to claim 4 having thestructure: ##STR123## wherein; A= ##STR124## G=hydrogen (H); R₉ =C₇ H₁₅; W=CH₂ ; Z=CH═CH; c=1; e=0; m=0; and n=4.
 10. A compound according toclaim 3 having the structure: ##STR125## wherein; A= ##STR126##G=hydrogen (H); R₉ =C₉ H₁₉ ; W=CH₂ ; Z=CH═CH; c=1; e=0; and n=4.
 11. Acompound according to claim 4 having the structure: ##STR127## wherein;A= ##STR128## G=hydrogen (H); R₉ =C₇ H₁₅ ; W=CH₂ ; Z=CH═CH; c=1; e=0;p=1; and q=1.
 12. A compound according to claim 3 having the structure:##STR129## wherein; A= ##STR130## G=hydrogen (H); R₉ =C₉ H₁₉ ; W=CH₂ ;Z=CH═CH; c=1; e=0; o=1; and p=0.
 13. A compound according to claim 4having the structure: ##STR131## wherein; A= ##STR132## G=hydrogen (H);R₉ =C₉ H₁₉ ; R₁₁ =CH₃ ; W=CH₂ ; Z=CH═CH; c=1; e=0; o=1;and p=1.
 14. Acompound according to claim 5 having the structure: ##STR133## wherein;A= ##STR134## R₉ =C₁₁ H₂₃ ; W=CH₂ ; Z=CH₂ CH₂ ; c=1 and e=0.
 15. Acompound according to claim 5 having the structure: ##STR135## wherein;A= ##STR136## R₉ =C₉ H₁₉ ; W=CH₂ ; Z=CH═CH; c=1 and e=0.